CN105322173A - Method for forming electrode, electrode, storage battery, and electric device - Google Patents
Method for forming electrode, electrode, storage battery, and electric device Download PDFInfo
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- CN105322173A CN105322173A CN201510283819.8A CN201510283819A CN105322173A CN 105322173 A CN105322173 A CN 105322173A CN 201510283819 A CN201510283819 A CN 201510283819A CN 105322173 A CN105322173 A CN 105322173A
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- 229910017052 cobalt Inorganic materials 0.000 description 1
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
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- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
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- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 description 1
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- 229910052731 fluorine Inorganic materials 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011245 gel electrolyte Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
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- 229910052738 indium Inorganic materials 0.000 description 1
- WPYVAWXEWQSOGY-UHFFFAOYSA-N indium antimonide Chemical compound [Sb]#[In] WPYVAWXEWQSOGY-UHFFFAOYSA-N 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
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- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- LGRLWUINFJPLSH-UHFFFAOYSA-N methanide Chemical compound [CH3-] LGRLWUINFJPLSH-UHFFFAOYSA-N 0.000 description 1
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- 239000011733 molybdenum Substances 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
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- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
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- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
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- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 150000004771 selenides Chemical class 0.000 description 1
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- 238000000926 separation method Methods 0.000 description 1
- 239000013464 silicone adhesive Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
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- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
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- 229910052718 tin Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- DZKDPOPGYFUOGI-UHFFFAOYSA-N tungsten(iv) oxide Chemical compound O=[W]=O DZKDPOPGYFUOGI-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
- H01M4/623—Binders being polymers fluorinated polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/049—Manufacturing of an active layer by chemical means
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
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- H01M4/667—Composites in the form of layers, e.g. coatings
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Carbon And Carbon Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a method for forming an electrode, the electrode, a storage battery, and an electric device. An electrode improved for achieving a storage battery having both a high electrode strength and favorable electrode conductivity is provided. The electrode includes graphene and a modified polymer in an active material layer or includes a layer substantially formed of carbon particles and an active material layer including a modified polymer over a current collector. The modified polymer has a poly(vinylidene fluoride) structure and partly has a polyene structure or an aromatic ring structure. The polyene structure or the aromatic ring structure is sandwiched between poly(vinylidene fluoride) structures.
Description
Technical field
A mode of the present invention relates to a kind of manufacture method of storage battery electrode.
Note, a mode of the present invention is not limited to above-mentioned technical field.The technical field of a mode of the invention that this specification etc. are disclosed relates to a kind of object, method or manufacture method.In addition, a mode of the present invention relates to a kind of operation (process), machine (machine), product (manufacture) or composition (compositionofmatter).Thus, more specifically, an example as the technical field of the mode of the present invention disclosed in this specification can enumerate semiconductor device, display unit, light-emitting device, electrical storage device, storage device, the driving method of these devices and the manufacture method of these devices.
Background technology
In recent years, along with popularizing rapidly of the portable electric appts such as mobile phone, smart mobile phone, E-book reader (e-book), portable game machine, the miniaturization of the secondary cell as its driving power, the requirement of high capacity are uprised.As the secondary cell that portable electric appts uses, what have the advantage such as high-energy-density, Large Copacity is that the storage battery of representative is utilized widely with lithium rechargeable battery.
The lithium rechargeable battery be widely spread because having high-energy-density in storage battery by: comprise cobalt acid lithium (LiCoO
2) or LiFePO4 (LiFePO
4) positive pole of isoreactivity material; By the negative pole that can carry out the material with carbon element such as the occlusion of lithium and the graphite of release and form; And will by LiBF
4, LiPF
6supporting electrolyte Deng lithium salts formation is dissolved in the nonaqueous electrolytic solution in the organic solvent such as ethylene carbonate or diethyl carbonate; Etc. formation.By making the lithium ion in secondary cell move between positive pole and negative pole through nonaqueous electrolytic solution, Lithium-ion embeding deintercalation is carried out the discharge and recharge of lithium rechargeable battery in the active material of both positive and negative polarity.Especially patent documentation 1 obtains high evaluation as the document of the lithium ion battery of the type reaction that illustrates that utilization is waved (rockingchair).
At this, the structure of the battery electrode be widely used is described.Electrode comprise on the collector of conductive support body comprise as active material inorganic compound particles and be used for the active material layer of adhesive of holding electrode shape.Use organic polymer as adhesive, but because adhesive also needs electrochemical stability, therefore often use the butadiene-styrene rubber (SBR) of one of the Kynoar (PVdF) or synthetic rubber of ferroelectric polymers.In addition, in order to evenly apply voltage to electrode, conductive auxiliary agent is added to active material layer.As conductive auxiliary agent, mainly use material with carbon element from the viewpoint of electrochemical stability, especially carbon black.Be included in because these adhesive and conductive auxiliary agent etc. stably keep the active material particle in the active material layer of shape to be in the state of electrical connection in parallel.
On the other hand, be insulant as the material that the adhesive can stablizing use is known, the material with carbon element used as conductive auxiliary agent has cohesive force hardly.The hole that electrode is required the electrolyte had for comprising transmission charge carrier ion or the flexibility had to a certain degree.In addition, if active material layer is formed fully thick by capacity increasing, then the problem easily making the reaction of the active material in electrode uneven because being applied in various Ohmic resistance can also be there is.
In view of the above problems, known following technology: high and easily occur, in the positive pole of oxidation reaction, to use the PVdF of ferroelectric polymers as adhesive at voltage, uses as conductive auxiliary agent the carbon black that particle diameter is little, typically acetylene black, makes dimensionally stable thus and guarantees conductivity.
As this example, patent documentation 2 discloses the way preventing the gelation easily carrying out PVdF because of carbon black.In addition, patent documentation 3 discloses the Ketjen black (trade mark at Japan registration) of the carbon black with higher order structure and the combination of PVdF or the copolymer containing PVdF.
[patent documentation 1] U.S. Reissue patent No. 4668595 specifications
[patent documentation 2] United States Patent (USP) No. 6200703 specifications
[patent documentation 3] U.S. Patent Application Publication No. 2010/0266882 specification
Along with the increase of energy requirement in recent years, being required consumingly to improve performance further, is namely higher cohesive force and lower electrode resistance.
Summary of the invention
In view of above-mentioned problem, one of object of a mode of the present invention is to provide a kind of manufacture method between adhesive and conductive auxiliary agent with interactional storage battery electrode.In addition, one of object of a mode of the present invention is, by using the storage battery electrode manufactured with this manufacture method, provides the storage battery that a kind of electric capacity of every electrode volume is large.
In view of above-mentioned problem, one of object of a mode of the present invention is, by making to have the macromolecule modified of Kynoar structure in active material layer, increasing itself and the interaction of Graphene containing aerobic, and improving pole strength.One of object of a mode of the present invention is, by making to have the macromolecule modified of Kynoar structure, making itself and the Graphene compound containing aerobic, and reducing electrode resistance.In addition, one of the object of a mode of the present invention comprises the storage battery of this electrode by providing a kind of and improve cycle characteristics.This modification instigates hydrogen fluoride to depart from from Kynoar structure.The structure of this modification refers to polyene structure or aromatic ring structure.
In view of above-mentioned problem, one of object of a mode of the present invention is, by make to comprise in the electrodes there is the macromolecule modified of Kynoar structure, increase this macromolecule and the interaction of material with carbon element that have passed through reduction treatment.One of object of a mode of the present invention is, by making to have the macromolecule modified of Kynoar structure, making itself and the material with carbon element compound that have passed through the process using reducing agent, and reducing electrode resistance.In addition, one of object of a mode of the present invention is, by making that there is the macromolecule modified of Kynoar structure, and the process using reducing agent is carried out to the material with carbon element contacted with collector, and reduce the interface resistance of active material layer and collector and improve interface binding intensity.This modification instigates hydrogen fluoride to depart from from Kynoar structure.The structure of this modification refers to polyene structure or aromatic ring structure.
In view of above-mentioned problem, one of object of a mode of the present invention is to provide the storage battery electrode that a kind of use has the macromolecule of the Kynoar structure of modification and the Graphene containing aerobic.One of object of a mode of the present invention is to provide and a kind ofly comprises the high molecular active material layer, carbon black layer and the electrode of collector that contacts with carbon black layer that comprise the Kynoar structure with modification.In addition, one of the object of a mode of the present invention is to provide a kind of storage battery comprising this electrode.
In view of above-mentioned problem, one of object of a mode of the present invention is to provide a kind of by making to comprise having the macromolecule modified of Kynoar structure and improving the manufacture method of the electrode of Strong degree in the electrodes.One of object of a mode of the present invention is to provide a kind of electrode to comprising macromolecule and the graphene oxide with Kynoar structure and carries out reduction treatment and improve the manufacture method with the electrode in uniform electrodes conduct path of pole strength.In addition, one of the object of a mode of the present invention is to provide and is a kind ofly applicable to the carbon black layer of reduction treatment, the collector contacted with carbon black layer and reducing agent by combination and the manufacture method of electrode that the adhesion strength of collector and active material layer is improved.
At this, Graphene has the material with carbon element hexagonal skeleton be made up of carbon being extended into plane crystal structure.Graphene is the material of monatomic that extracts from graphite crystal, there is fabulous electrical characteristics, mechanical property and chemical characteristic, therefore the various field such as field-effect transistor, high sensitivity transducer, high efficiency solar cell, nesa coating of new generation being applied to high mobility is expected to, noticeable.
In this manual, Graphene comprises single-layer graphene or the two-layer above and multi-layer graphene of less than 100 layers.Single-layer graphene refers to the carbon point sub-pieces of the monoatomic layer with π key.A graphene film is called graphene platelet.In addition, graphene oxide refers to the compound that above-mentioned Graphene is oxidized.In addition, when forming Graphene (being also called the disengaging reaction in graphene oxide) when making graphene oxide reduce, the oxygen be included in graphene oxide not necessarily all departs from, and wherein a part remains in Graphene sometimes.In the oxygen containing situation of Graphene bag, the ratio of the oxygen in the Graphene entirety utilizing XPS (X-rayPhotoelectronSpectroscopy:X ray photoelectron spectroscopy) to measure is more than 2atom% and below 20atom%, is preferably more than 3atom% and below 15atom%.In addition, the graphene oxide be reduced, namely ReducedGrapheneOxide (RGO: redox graphene) is also included within Graphene.
In view of above-mentioned problem, the problem of a mode of the present invention is to provide the electrical storage device of a kind of electrode of novelty, novel secondary cell or novelty.Note, the description of above-mentioned purpose is not hindered to the existence of other objects.Note, a mode of the present invention does not need to realize all above-mentioned purposes.Object except above-mentioned purpose is apparent from the description of specification, accompanying drawing, claims etc., and can extract out from described description.
So a mode of the present invention is a kind of electrode, comprises active material particle, Graphene and have the macromolecule of Kynoar structure, wherein, the polymer moiety with Kynoar structure has polyene structure or aromatic ring structure.
A mode of the present invention is a kind of electrode, comprising: comprise active material particle and have the high molecular active material layer of Kynoar structure; And the collector of layer comprising metal forming and be made up of carbon particle in fact, wherein, the polymer moiety with Kynoar structure has polyene structure or aromatic ring structure.
A mode of the present invention is a kind of electrode, comprising: comprise active material particle, Graphene and have the high molecular active material layer of Kynoar structure; And the collector of layer comprising metal forming and be made up of carbon particle in fact, wherein, the polymer moiety with Kynoar structure has polyene structure or aromatic ring structure.
A mode of the present invention is the electrode of the arbitrary structure had in said structure, and wherein polyene structure or aromatic ring structure are between two Kynoar structures.
A mode of the present invention is the electrode of the arbitrary structure had in said structure, and wherein Graphene is containing aerobic, and the ratio of the oxygen measured by XPS is more than the 1atm% of Graphene entirety and below 20atm%.
A mode of the present invention a kind ofly comprises the electrode of the arbitrary structure had in said structure and electrolytical storage battery.
A mode of the present invention is the electronic equipment comprising storage battery, framework, display unit or the switch with above-mentioned each structure.
A mode of the present invention is a kind of manufacture method of electrode, comprises the steps: to be formed on a current collector the high molecular active material layer comprising active material particle, graphene oxide and have Kynoar structure; And collector to be soaked in containing the aqueous solution of reducing agent and hydrogen fluoride is departed from from the macromolecule with Kynoar structure, make this macromolecule modified thus and form electrode.
A mode of the present invention is a kind of manufacture method of electrode, comprises the steps: the layer be made up of carbon particle to be in fact coated in metal forming to form collector; Form the high molecular active material layer comprising graphene oxide and there is Kynoar structure on a current collector; And collector to be soaked in containing the aqueous solution of reducing agent and hydrogen fluoride is departed from from the macromolecule with Kynoar structure, make this macromolecule modified thus and form electrode.
A mode of the present invention is a kind of manufacture method of electrode of the arbitrary structure had in said structure, and wherein reducing agent has more than-5.0eV and the material of lumo energy below-3.8eV.
A mode of the present invention is a kind of manufacture method of electrode of the arbitrary structure had in said structure, and wherein reducing agent has more than-0.4V for the current potential of saturated calomel electrode and the material of reduction potential below+0.8V.
A mode of the present invention is a kind of manufacture method of electrode, comprises the steps: to be formed on a current collector the compound particle comprising and comprise active material and Graphene and the high molecular active material layer with Kynoar structure; And active material layer soaked in pure water or the aqueous solution, hydrogen fluoride is departed from from the macromolecule with Kynoar structure, make this macromolecule modified thus and form electrode.
A mode of the present invention is a kind of manufacture method of electrode, comprises the steps: the layer be made up of carbon particle to be in fact coated in metal forming to form collector; Form the high molecular active material layer comprising active material particle and there is Kynoar structure on a current collector; And active material layer soaked in pure water or the aqueous solution, make hydrogen fluoride depart from from the macromolecule with Kynoar structure and form electrode.
A mode of the present invention is a kind of manufacture method of electrode of the arbitrary structure had in said structure, wherein produces polyene structure or aromatic ring structure by making hydrogen fluoride depart from from Kynoar structure.
A mode of the present invention is a kind of manufacture method of electrode of the arbitrary structure had in said structure, and wherein the pKb of the aqueous solution is expressed with pKa-4 < pKb < pKa+4.
A mode of the present invention is a kind of manufacture method of electrode of the arbitrary structure had in said structure, and wherein the pH of the aqueous solution is expressed with 5 < pH < 9.
By a mode of the present invention, a kind of pole strength can be provided high and the electrode that conductance is high.
By a mode of the present invention, a kind of electrode with stronger caking property between collector and active material layer and stable low electrode interface resistance can be provided.
By a mode of the present invention, a kind of storage battery of cycle characteristics that there is larger electrode capacitance, high speed charge-discharge characteristic and improve can be provided.
By a mode of the present invention, the electrical storage device of a kind of electrode of novelty, novel secondary cell or novelty can be provided.Note, a mode of the present invention is not limited to these effects.A mode of the present invention according to circumstances has effect other than the above sometimes.A mode of the present invention does not have these effects sometimes according to situation or situation.
Accompanying drawing explanation
Figure 1A to Fig. 1 C is the figure that storage battery electrode is described.
Fig. 2 is the figure of the molecular separating force of the graphene oxide that a mode of the present invention is described.
Fig. 3 is the figure of the modified high-molecular that a mode of the present invention is described.
Fig. 4 A and Fig. 4 B is the figure that Coin shape storage battery is described.
Fig. 5 is the figure that laminated-type storage battery is described.
Fig. 6 A and Fig. 6 B is the figure that laminated-type storage battery is described.
Fig. 7 A and Fig. 7 B is the figure that cylinder battery is described.
Fig. 8 is the figure of the example that electronic equipment is described.
Fig. 9 A to Fig. 9 C is the figure of the example that electronic equipment is described.
Figure 10 A and Figure 10 B is the figure of the example that electronic equipment is described.
Figure 11 A and Figure 11 B is the figure of the analysis result that particle size distribution is shown.
Figure 12 is the figure of the battery behavior of the battery that the electrode using a mode of the present invention is shown.
Figure 13 A to Figure 13 D is the figure that ToF-SIMS analysis result is shown.
Figure 14 A to Figure 14 D is the figure that ToF-SIMS analysis result is shown.
Figure of abstract of the present invention is Fig. 3.
Embodiment
Below, with reference to accompanying drawing, execution mode is described.Note, execution mode can be implemented in a number of different ways, person of an ordinary skill in the technical field can understand a fact easily, is exactly that its mode and detailed content can be transformed to various form and not depart from aim of the present invention and scope thereof.Therefore, the present invention should not be interpreted as only being limited in the content described in execution mode shown below.
Execution mode 1
In the present embodiment, with reference to Figure 1A to Fig. 1 C, the manufacture method according to the storage battery electrode of a mode of the present invention is described.
Figure 1A is the stereogram of storage battery electrode 100, and Figure 1B is the longitdinal cross-section diagram of storage battery electrode 100.Figure 1A illustrates storage battery electrode 100 with rectangular patch, but the shape of storage battery electrode 100 is not limited to this, suitably can select arbitrary shape.In Figure 1A and Figure 1B, be only formed with active material layer 102 in a face of collector 101, but also can at the two-sided formation active material layer 102 of collector 101.In addition, active material layer 102 does not need the whole surface being formed at collector 101, and suitably arranges the non-coated area such as the region for being connected to electrode tabs.
Only otherwise in electrical storage device, cause significant chemical change and present high conductivity, just the collector for plus plate current-collecting body and negative current collector is had no particular limits.Such as, the alloy (stainless steel etc.) of the metals such as gold, platinum, iron, nickel, copper, aluminium, titanium, tantalum, manganese and these metals can be used.In addition, also can add silicon, neodymium, scandium, molybdenum etc. to these metal or alloy and improve thermal endurance.In addition, carbon, nickel or titanium etc. also can be used to cover these metal or alloy.In addition, collector can suitably have comprise foil-like, sheet, tabular, netted, cylindric, coiled type, punch metal are netted, draw metal is netted, the various shapes of cellular and non-woven fabrics etc.Further, in order to improve the compactness with active material, collector can also have small concavo-convex on its surface.In addition, the thickness of collector is preferably more than 5 μm and less than 30 μm.
Fig. 1 C is the longitdinal cross-section diagram of active material layer 102.Active material layer 102 comprises granular active material 103, as the graphene platelet 104 of the Graphene of conductive auxiliary agent and binding agent (also referred to as binder, not shown).
In the longitudinal cross-section of active material layer 102, as shown in Figure 1 C, the graphene platelet 104 of sheet is roughly evenly dispersed in the inside of active material layer 102.In fig. 1 c, although schematically represent graphene platelet 104 with thick line, in fact graphene platelet 104 is for having the film of the thickness of the single or multiple lift of carbon molecule.Because multiple graphene platelet 104 is to surround or cover the mode of multiple granular active material 103 or formed in the mode on the surface being attached to multiple granular active material 103, so graphene platelet 104 contacts with active material 103 forming surface.In addition, also forming surface contact mutually between graphene platelet 104, so form three-dimensional conductive network by multiple graphene platelet 104.
This is because when forming Graphene, the cause of the graphene oxide using the dispersiveness in polar solvent high.This solvent is made to volatilize from the decentralized medium comprising homodisperse graphene oxide and remove, and graphene oxide reduction is formed Graphene, so the graphene platelet 104 remained in active material layer 102 partly overlaps mutually, disperse in the mode of forming surface contact, form conductive path thus.
Therefore, be different from and form the existing particulate conductive auxiliary agents such as the acetylene black of point cantact with active material, Graphene can realize the high face contact of contact probability, so can use the conductive path in a small amount of conductive auxiliary agent formation granular active material 103 and graphene platelet 104.Therefore, the ratio shared by active material 103 in active material layer 102 can be increased.Thus, the discharge capacity of storage battery can be increased.
As active material 103, the carrier ions such as lithium ion can be used to embed and the material of deintercalation.By carrying out in a suitable approach pulverizing, granulation and classification, average grain diameter and the domain size distribution of active material can be controlled.Therefore, although schematically show spherical active material 103 in fig. 1 c, this shape is not limited to.
The average grain diameter of the primary particle of active material 103 is below 500nm, is preferably more than 50nm and below 500nm.In order to make graphene platelet 104 contact with this granular active material 103 forming surface multiple, a length of side of graphene platelet 104 is preferably more than 50nm and less than 100 μm, is more preferably more than 800nm and less than 20 μm.
When using positive active material as active material 103, lithium ion can be used to embed and the material of deintercalation, such as, can use the material etc. with olivine-type structure, rocksalt-type structure, spinel structure, NASICON type crystalline texture.
Such as, as the material of positive active material, LiFeO can be used
2, LiCoO
2, LiNiO
2, LiMn
2o
4, V
2o
5, Cr
2o
5, MnO
2deng compound.
Or, can use have olivine-type structure containing lithium composite phosphate.Should contain lithium composite phosphate can with general formula LiMPO
4(M be in Fe, Mn, Co and Ni more than one) represents.As general formula LiMPO
4exemplary, can LiFePO be enumerated
4, LiNiPO
4, LiCoPO
4, LiMnPO
4, LiFe
ani
bpO
4, LiFe
aco
bpO
4, LiFe
amn
bpO
4, LiNi
aco
bpO
4, LiNi
amn
bpO
4(a+b is less than 1,0 < a < 1,0 < b < 1), LiFe
cni
dco
epO
4, LiFe
cni
dmn
epO
4, LiNi
cco
dmn
epO
4(c+d+e is less than 1,0 < c < 1,0 < d < 1,0 < e < 1), LiFe
fni
gco
hmn
ipO
4(f+g+h+i is less than 1,0 < f < 1,0 < g < 1,0 < h < 1,0 < i < 1) etc. lithium metal tripolyphosphate compound.
Or, general formula Li can be used
(2-j)mSiO
4lithium-containing transition metal silicate such as (M are more than one in Fe (II), Mn (II), Co (II) and Ni (II), 0≤j≤2).As general formula Li
(2-j)mSiO
4exemplary, can Li be enumerated
(2-j)feSiO
4, Li
(2-j)niSiO
4, Li
(2-j)coSiO
4, Li
(2-j)mnSiO
4, Li
(2-j)fe
kni
lsiO
4, Li
(2-j)fe
kco
lsiO
4, Li
(2-j)fe
kmn
lsiO
4, Li
(2-j)ni
kco
lsiO
4, Li
(2-j)ni
kmn
lsiO
4(k+l is less than 1,0 < k < 1,0 < l < 1), Li
(2-j)fe
mni
nco
qsiO
4, Li
(2-j)fe
mni
nmn
qsiO
4, Li
(2-j)ni
mco
nmn
qsiO
4(m+n+q is less than 1,0 < m < 1,0 < n < 1,0 < q < 1), Li
(2-j)fe
rni
sco
tmn
usiO
4(r+s+t+u is less than 1,0 < r < 1,0 < s < 1,0 < t < 1,0 < u < 1) etc. lithium metal silicate compound.
In addition, as active material 103, can use with general formula A
xm
2(XO
4)
3the NASICON type compound that (A=Li, Na, Mg, M=Fe, Mn, Ti, V, Nb, Al, X=S, P, Mo, W, As, Si) represents.As NASICON type compound, Fe can be enumerated
2(MnO
4)
3, Fe
2(SO
4)
3, Li
3fe
2(PO
4)
3deng.In addition, as positive active material, can use: with general formula Li
2mPO
4f, Li
2mP
2o
7, Li
5mO
4the compound that (M=Fe, Mn) represents; NaF
3, FeF
3in perovskite fluoride; TiS
2, MoS
2deng metal chalcogenide compound (sulfide, selenides, tellurides); LiMVO
4etc. the material of crystal structure with inverse spinel structure; Barium oxide class (V
2o
5, V
6o
13, LiV
3o
8deng); Mn oxide; And the material such as organosulfur compound.
In addition, when the alkali metal ion outside lithium ion, alkaline-earth metal ions are used as carrier ion, as positive active material, also can use with alkali metal (such as, sodium, potassium), the carrier ion of alkaline-earth metal (such as, calcium, strontium, barium, beryllium, magnesium) etc. the compound that replaces above-mentioned lithium compound, obtain containing the lithium in lithium composite phosphate and lithium-containing transition metal silicate.
The average grain diameter of positive active material is preferably such as more than 5nm and less than 50 μm.
When using negative electrode active material as active material 103, carbon class material, alloy type material etc. can be used.
As carbon class material, graphite, easily graphitized carbon (graphitizingcarbon) (soft carbon), difficult graphitized carbon (non-graphitizingcarbon) (hard carbon), carbon nano-tube, Graphene, carbon black etc. can be enumerated.
As graphite, there are the native graphites such as Delanium or spheroidizing native graphite such as carbonaceous mesophase spherules (MCMB), coke-based Delanium (coke-basedartificialgraphite), asphaltic base Delanium (pitch-basedartificialgraphite).
When generating lithium-compound between graphite layers in Lithium-ion embeding graphite, the current potential of graphite becomes the electronegative potential with lithium metal same degree.Thus, lithium rechargeable battery can have high working voltage.Moreover graphite tool has the following advantages: the capacity of per unit volume is higher; Change in volume with discharge and recharge is little; Cheap; Fail safe is higher than lithium metal; Deng.
In addition, as negative electrode active material, also can use can by taking off with the alloying of carrier ion the material that alloying reaction carries out discharge and recharge.Such as when carrier ion is lithium ion, the material of at least one comprised in Mg, Ca, Ga, Si, Al, Ge, Sn, Pb, Sb, Bi, Ag, Zn, Cd, As, Hg and In etc. can be used.The Capacity Ratio carbon of this element is high, and especially the theoretical capacity of silicon is significantly high, i.e. 4200mAh/g.Thus, preferably silicon is used for negative electrode active material.As the material using this element, such as, SiO, Mg can be enumerated
2si, Mg
2ge, SnO, SnO
2, Mg
2sn, SnS
2, V
2sn
3, FeSn
2, CoSn
2, Ni
3sn
2, Cu
6sn
5, Ag
3sn, Ag
3sb, Ni
2mnSb, CeSb
3, LaSn
3, La
3co
2sn
7, CoSb
3, InSb and SbSn etc.
In addition, as negative electrode active material, oxide such as titanium dioxide (TiO can be used
2), Li-Ti oxide (Li
4ti
5o
12), niobium pentoxide (Nb
2o
5), tungsten oxide (WO
2), molybdenum oxide (MoO
2) etc.
In addition, as negative electrode active material, what can use the nitride of lithium and transition metal has Li
3the Li of N type junction structure
3-xm
xn (M=Co, Ni, Cu).Such as, Li
2.6co
0.4n
3present large charge/discharge capacity (900mAh/g, 1890mAh/cm
3).
When using the nitride of lithium and transition metal, in negative electrode active material, comprise lithium ion, therefore can by this negative electrode active material and the V not comprising lithium ion being used as positive active material
2o
5, Cr
3o
8deng combination of materials.Noting, when the material containing lithium ion is used as positive active material, by making the lithium ion deintercalation be included in positive active material in advance, also can use the nitride of lithium and transition metal as negative electrode active material.
In addition, also negative electrode active material can be used as by causing the material of conversion reaction.Such as, cobalt oxide (CoO), nickel oxide (NiO), iron oxide (FeO) etc. are not used for negative electrode active material with the oxide of the transition metal of lithium generation alloying reaction.As the material causing conversion reaction, Fe can also be enumerated
2o
3, CuO, Cu
2o, RuO
2, Cr
2o
3deng oxide, CoS
0.89, NiS, CuS sulfides, Zn
3n
2, Cu
3n, Ge
3n
4deng nitride, NiP
2, FeP
2, CoP
3deng phosphide, FeF
3, BiF
3in fluoride.Note, because the current potential of above-mentioned fluoride is high, so also can positive active material be used as.
In the present embodiment, Graphene is used as conductive auxiliary agent.Graphene is obtained by making graphene oxide reduce.Graphene oxide can be manufactured by various synthetic methods such as Hummers method, ModifiedHummers method or graphite-like oxidations.
Such as, Hummers method is the method by making the graphite oxidations such as flaky graphite form graphite oxide.The graphite oxide formed be graphite partially oxidized and with the functional groups such as carbonyl, carboxyl, hydroxyl and being formed, the crystallinity of graphite reduces, and interfloor distance becomes large.Thus, by carrying out ultrasonic wave process etc., can interlaminar separation be made relatively easily and obtain graphene oxide.
In addition, a length of side (also referred to as scale size) of graphene oxide for more than 50nm and less than 100 μm, is preferably more than 800nm and less than 20 μm.
In the storage battery electrode of a mode according to the present invention, the conductive auxiliary agent as electrode uses this Graphene.But, when using Graphene or the Graphene (as the abbreviation of ReducedGrapheneOxide also referred to as RGO) that makes graphene oxide reduce in advance and formed and active material and adhesive is mixing manufacture storage battery electrode time, dispersiveness due to Graphene, RGO is lower and be gathered in electrode, causes being difficult to obtain sufficient battery behavior.
On the other hand, when the raw material of the conductive auxiliary agent as electrode uses graphene oxide, be arranged through graphene oxide, active material and the binding agent mixing and mixture obtained in polar solvent on a current collector, then by reduction treatment, graphene oxide is reduced, can Graphene be formed thus.When utilizing said method to manufacture electrode, in the active material layer containing active material and binding agent, form the conductance network of Graphene.Its result, can form the electrode comprising the high conductivity active material layer be electrically connected to each other by Graphene between active material.
This is because the graphene oxide that such raw material as Graphene uses as described in Figure 2 is the polar substances with functional groups such as epoxy radicals, carbonyl, carboxyl, hydroxyls.Because the oxygen in the functional group of graphene oxide is electronegative in polar solvent, therefore, be not easy to flock together between different graphene oxide thin slices.On the other hand, graphene oxide and the interaction for mixing polar solvent or active material are comparatively large, and the functional groups such as the epoxy radicals that graphene oxide has and polar solvent interact.Thus, can think: because the gathering between graphene oxide thin slice is obstructed, its result, dispersed in decentralized medium have graphene oxide.In addition, because graphene oxide thin slice is thinner, molecular separating force is large graphene oxide is especially easily adhered to the active material particle containing aerobic, and, because graphene oxide thin slice is not easy mutually to be bonded together, the tendency that the gathering between having thus containing the active material particle of aerobic is inhibited.
When the raw material as conductive auxiliary agent uses graphene oxide, although graphene oxide has good dispersiveness relative to decentralized medium, because conductivity is extremely low, so only utilize graphene oxide cannot play the effect of conductive auxiliary agent.But graphene oxide has the more stable skeleton deriving from Graphene, so conductivity can be given to graphene oxide relatively easily by reduction treatment.
At this, as the method for reducing of graphene oxide, mainly can enumerate: the reduction (thermal reduction) utilizing heating; In the electrolytic solution electrode is applied to the electrochemical reduction (electrochemical reduction) of the current potential that graphene oxide is reduced; Use the reduction (electronation) of reducing agent.
When carrying out thermal reduction, should be noted that and not make other materials occur to decompose or go bad.
When carrying out electrochemical reduction, should be noted that, under electrolyte does not make the condition of the material dissolves of formation storage battery electrode, sufficiently uniformly voltage be applied to electrode.
When carrying out electronation, should be noted that and not make because of reducing agent or reducing solution active material or collector dissolve or go bad.
About the method for reducing of these graphene oxides, will explain later.
Above-mentioned material is used to manufacture electrode.
First, mixed oxidization Graphene and active material particle, add 1-Methyl-2-Pyrrolidone (NMP) or dimethyl formamide (DMF) polar solvent, and mixingly modulate paste mixture.When especially using the material containing aerobic as active material 103, active material particle and graphene oxide can be made to disperse equably, and can be little at aggregate particle size, namely assemble by mixing under the state removed.In addition, the viscosity of the degree freely do not flowed under static condition is referred at this paste.
Obtained paste mixture is carried out dry thick mixing.At this, dry thick mixing refer to high viscosity carry out mixing because there is larger shearing force, therefore easily there is active material or the dispersion of graphene oxide and the stripping of graphene oxide.As carrying out dry thick mixing means, the device such as planetary mixer or kneader can be used.
Moreover, to carry out dry thick mixing after paste mixture add solvent and adhesive adjustment viscosity, form pulp-like mixture.At this, pulp-like refers to the viscosity of the degree also under static condition with mobility.Carry out mixing means as to pulp-like mixture, can use and stir the various mixer such as defoamer or homogenizer (dissolver).
At this, use the macromolecule with Kynoar structure as adhesive.As the macromolecule with Kynoar structure, can enumerate Kynoar (PVdF), comprise the copolymer of PVdF, such as, be the copolymer of PVdF and polytetrafluoroethylene (PTFE).PVdF is once react with alkali, and hydrofluoric disengaging reaction just occurs chainly.By using copolymer, this chain reaction can be suppressed.
Note, different devices can be used according to viscosity, planetary mixer etc. also can be utilized only to make viscosity gradually change and mixing.In addition, when stirring with flank speed, even if viscosity is low also fully can produce shearing force, even if so start in the slurry state without the mixing of paste state mixing also can be mixing equably.
Pulp-like mixture is coated on a face or two-sided of collector.As coating method, such as, slit can be used to extrude (slot-die) mode, intaglio plate (gravure) mode, scraper (blade) mode and combine the method for these modes.
Then, adopt the method such as aeration-drying or drying under reduced pressure to make solvent evaporates, form the electrode comprising active material layer 102 and collector 101.Aeration-drying such as can use more than 50 DEG C and the hot blast of less than 180 DEG C.Thus, the polar solvent volatilization be included in active material layer 102 is made.
At this, the content of graphene oxide is more than the 0.1wt% of the mixture total weight amount of graphene oxide, active material, conductive auxiliary agent and adhesive and below 10wt%, be preferably more than 0.1wt% and below 5wt%, be more preferably more than 0.2wt% and below 2wt%, more preferably more than 0.2wt% and below 1wt%.On the other hand, in active material layer, the content of Graphene is more than the 0.05wt% of the total weight of active material layer and below 5wt%, be preferably more than 0.05wt% and below 2.5wt%, be more preferably more than 0.1wt% and below 1wt%, more preferably more than 0.1wt% and below 0.5wt%.This is because the weight of Graphene approximately reduces half due to the reduction of graphene oxide.The content of adhesive is more than 0.5wt% and below 20wt%, is preferably more than 1wt% and below 10wt%.
Roll-in method or the isobaric compression method of dull and stereotyped platen press can be utilized to press this active material layer 102 and make its densification.
Then, this active material layer 102 is made to react in the solution (being also called reducing solution) containing reducing agent.By this reaction, the graphene oxide be included in active material layer is made to reduce and form Graphene.Note, the oxygen be included in graphene oxide is not necessarily all released, and a part for oxygen also can remain in Graphene.When Graphene is containing aerobic, the ratio of the oxygen measured by XPS is more than the 2atm% of Graphene entirety and below 20atm%, is preferably more than 3atm% and below 15atm%.This reduction treatment preferably more than room temperature and less than 150 DEG C carry out.
As solute, can use and there is more than-5.0eV and the material of lumo energy below-3.8eV.Or, can use and there is more than-1.3V and (vs.SCE) below+0.8V, be preferably more than-0.4V and the reducing agent of the reduction potential of (vs.SCE) below+0.8V.As concrete reducing agent, ascorbic acid, hydrazine, dimethylhydrazine, hydroquinones, sodium borohydride (NaBH can be enumerated
4), TBAB (TBAB), N, N-diethyl hydroxylamine and their derivative.Especially when the reducing agent using reducing power more weak, just not on the impact of active material.In addition, be not easy react with the moisture in solvent or air and decompose, so tail off to the restriction that reduction treatment environment or solvent are selected.
Polar solvent can be used as solvent.As long as the solvent that reducing agent can be made to dissolve just not limiting material.Such as, the mixed liquor of any one or more in water, methyl alcohol, ethanol, acetone, oxolane (THF), DMF, NMP and dimethyl sulfoxide (DMSO) (DMSO) can be used.Especially, when using water, industrial advantage is larger.In addition, by using water, can Reaction time shorten.
Preferably, the above-mentioned reducing solution comprising solvent and solute is roughly neutrality or slightly alkaline.That is, acid ionization constant pKa and dissociation constant of a base pKb preferably has following relation: pKb < pKa+4.Thus, easily there is the modification of the Kynoar structure in macromolecule.In addition, pKb > pKa-4 is preferably, because the too much modification of Kynoar structure more easily can be suppressed.Be more preferably pKa-2 < pKb < pKa+2, now can more easily suppress high molecular modification.When reducing solution is the aqueous solution, be preferably 4 < pH < 10, be more preferably 5 < pH < 9, more preferably 6 < pH < 8.Also base reagent can be added to reducing solution.
Then, electrode is washed.The solvent of reducing solution can be used as cleaning solution.The reducing agent stayed can be removed by washing.Further, can also promote to depart from reaction in RGO.Moreover, except reduction treatment operation, still can make macromolecule modified in this washing procedure.Can think: the reducing agent do not departed from by making to be added or proton depart from, the promotion of the disengaging reaction in RGO occurs.Therefore, also the reagent easily making proton depart from can be added a little.Usually, keep reducing solution to a certain degree in the electrodes, so the cleaning solution after using comprises reducing agent with the concentration below the concentration of the reducing solution used in reduction treatment.Washed by repeated multiple times, the concentration of the reducing agent in the cleaning solution and electrode comprised after a procedure can be reduced.In addition, by adding alkali to cleaning solution, high molecular modification can be promoted.Especially, when using pure water, easily promoting the disengaging reaction in RGO and high molecular modified-reaction, and there is larger industrial advantage, so be preferred.
This high molecular modified-reaction is hydrofluoric disengaging reaction typically, and macromolecule modified the becoming with Kynoar structure has Kynoar structure and the macromolecule partly with the aromatic ring structure of polyene structure or cyclized structure.In other words, by carry out dehydrofluorination make polyvinylidene fluoride modified and become the aromatic ring structure in its main chain with polyene structure or cyclized structure by the Kynoar of partial dehydrogenfluoride.Fig. 3 illustrates an example of the high molecular molecular structure of modification.The polyene structure produced or the aromatic ring structure of cyclized structure are clipped between unmodified Kynoar structure.Noting, is with (CH) at this said polyene structure
nthe part-structure that (n > 3) represents.Aromatic ring structure is the aryl comprising polycyclic aromatic hydrocarbon base, and comprises phenyl, xenyl or naphthyl.Kynoar structure is with (CF
2cH
2)
nthe part-structure represented, comprises the monomer of more than 100 in macromolecule, but monomer structure identical in the polymer of such as random copolymer is not necessarily continuous.In addition, the ratio of modification, the summation of the carbon number ratio of namely produced aromatic ring structure and polyene structure lower than Kynoar structure carbon number ratio 5%.
Moreover, the electrode after heated scrub.The heating of electrode is preferably under reduced pressure carried out.This heating process is such as preferably in a vacuum with more than 50 DEG C and the temperature of less than 200 DEG C carries out more than 1 hour and less than 48 hours.By carrying out this heating process, the polar solvent or moisture that are present in active material layer 102 can be removed.In addition, the reduction of RGO can be promoted.By this process or other thermal condensations etc., pole strength can be improved.
Roll-in method or the isobaric compression method of dull and stereotyped platen press can be utilized to press obtained electrode and make its densification.Pressing both all can be carried out for twice before and after reduction treatment, can carry out again before or after reduction treatment.In addition, be specified size by the electrode forming obtained, make storage battery electrode thus.Especially the situation being mixed into moisture in storage battery becomes larger problem, therefore preferably removes moisture limit below in reduced atmosphere and presses, but preferably presses under air atmosphere from the viewpoint process.Therefore, under reduced pressure heating electrode after reduction treatment, then presses this electrode, thus is configured as specified size under air atmosphere.In addition, preferably, the electrode that obtains under reduced pressure is heated further to remove moisture fully.
The macromolecule of modification and the caking property of RGO are improved, and therefore can improve electrode Strong degree.In addition, because RGO disperses equably with active material particle in electrode, so voltage can be applied equably to electrode integral.Therefore, the situation of the active material particle polarization of the part in little generating electrodes, and capacity is improved.Because seldom occur in the preferential situation that cell reaction occurs in the particle of a part, so cycle characteristics is also improved.Closely be bonded together by adhesive and RGO between active material particle, even if therefore such as because of the decomposition of electrolyte, the interface resistance increase of active material is also not easy to have an impact.This means to suppress the ability of the internal resistance change of battery strong, therefore, it is possible to improve cycle characteristics or storage characteristic.
By above-mentioned steps, can manufacture comprise the Kynoar structure with modification macromolecule, Graphene, active material particle storage battery electrode 100.
Note, a mode of the present invention can be applied to various electrical storage device.As an example of electrical storage device, battery, primary cell, secondary cell, lithium rechargeable battery (also comprising lithium ion polymer secondary cell), lithium-air battery can be enumerated.As other examples of electrical storage device, capacitor can be enumerated.
Present embodiment can suitably combine with other execution modes and implement.
Execution mode 2
In the present embodiment, the manufacture method of the storage battery electrode of the interfacial adhesion improving active material layer and collector is described.
First, modulation comprises active material particle, has the pulp-like mixture of the macromolecule of Kynoar structure and conductive auxiliary agent.At this, conductive auxiliary agent is had no particular limits, can carbon black be used, acetylene black or Ketjen black (trade mark at Japan registration) etc. wherein can be used to have the carbon black of higher order structure.Or, also can use above-mentioned Graphene etc.
The metal forming covered by the layer be made up of carbon particle is in fact used for collector.About the kind of metal forming, can with reference to execution mode 1, but the feature of present embodiment is metal forming is covered by the layer be made up of carbon particle in fact.The layer be made up of carbon particle in fact not necessarily covers collector tight, and easy with island covering collector, the metallic member of collector exposes.In addition, this layer be made up of carbon particle in fact also can comprise the carbon particle of the size close to graphite, can also only be made up of the carbon black below sub-micron.By modulation, carbon particle be scattered in the dispersion liquid in solvent and by this dispersed liquid coating in collector, the layer be made up of carbon particle in fact can be formed.The dispersion liquid being dispersed with carbon particle comprises with the ratio of below 1wt% or does not include organic polymer completely.The aqueous solution being dispersed with carbon black can be used as the dispersion liquid being dispersed with carbon particle.As process for dispersing, the method etc. of the alkali such as known interpolation ammonia.As carbon particle, preferably use carbon black.The thickness of the layer be made up of carbon particle is about less than 2 μm.
The pulp-like mixture comprising active material particle is coated on the collector that covered by the layer that is made up of carbon particle in fact, forms active material layer thus.Coating method or be used for making the heating means of solvent evaporates can use the method same with execution mode 1.
Obtained electrode is soaked in polar solvent.Thus, can make, in active material layer, there is the macromolecule modified of Kynoar structure.This modification is hydrofluoric disengaging typically, and macromolecule modified the becoming with Kynoar structure has Kynoar structure and the macromolecule partly with the aromatic ring structure of polyene structure or cyclized structure.When utilizing the pulp-like mixture comprising graphene oxide to use Graphene as conductive auxiliary agent, the reduction operation of graphene oxide and the modified process of Kynoar structure can be carried out in one step.As polar solvent, the alcohols such as water or ethanol can be used.Electrode also can be comprised pH adjusting agent by the liquid soaked into, but pH now also not necessarily must be made to change.This is because the hydrofluoric acid departed from by modification is acid.Certainly, with other process carry out high molecular modification simultaneously time, also pH (or pKa) can be changed according to the process carried out simultaneously.High molecular modification is more easily carried out for during alkalescence by the liquid soaked at electrode, even if but also can carry out this modification according to time or temperature at this liquid for when neutral or faintly acid.Note, if high molecular modification is excessive, then causes the decline of high molecular gelation or adhesive function, therefore, preferably only make high molecular a part of modification.Now, the polyene structure of generation or the aromatic ring structure of cyclized structure are clipped in unmodified Kynoar structure.In addition, as mentioned above, be with (CH) at this said polyene structure
nthe part-structure that (n > 3) represents.Aromatic ring structure is the aryl comprising polycyclic aromatic hydrocarbon base, and it comprises phenyl, xenyl, naphthyl.Kynoar structure is with (CF
2cH
2)
nthe part-structure represented, comprises the monomer of more than 100 in macromolecule, but monomer structure identical in the polymer of such as random copolymer is not necessarily continuous.
After carrying out modification, heating electrode, and make the solvent evaporates that comprises.After carrying out modification, can suitably wash.Heating can under atmospheric pressure be carried out, and also can under reduced pressure carry out.So that the heating under atmospheric pressure and the heating under decompression can be combined at different temperature.
Roll-in method or the isobaric compression method of dull and stereotyped platen press is preferably utilized to press obtained electrode and make its densification.Pressing is preferably all carried out for twice, or carry out before or after modification before and after modification.Especially the situation being mixed into moisture in storage battery becomes larger problem, therefore preferably removes moisture limit below in reduced atmosphere and presses, but preferably presses under air atmosphere from the viewpoint process.Preferably heat after modification and press electrode, and more carefully making water or solvent evaporates.
Finally, be specified size by electrode forming, manufacture storage battery electrode thus.
At the near interface of collector, between metal forming and active material layer, accompany the layer (being also called cover layer) be made up of carbon particle in fact.Metal forming has oxide skin(coating) on its surface under many circumstances, and oxide skin(coating) produces interface resistance.By cover layer is formed at metal foil surface, the metal foil surface that cover layer contacts is reduced, so be not easy to form oxide skin(coating), and produces interface resistance hardly.
On the other hand, be contained in the middle of the material being used as carbon particle in cover layer, the material that molecular separating force is good is less.Therefore, such as, in cover layer during mixed polymer, the coating condition being used for being formed tectal mixed liquor improves.In addition, the interface Strong degree of electrode can be improved.But when using present embodiment, be formed with the structure with the conjugated pi bonding identical with the carbon particle be included in cover layer in the macromolecule that active material layer comprises, therefore active material layer and the tectal Strong degree that bonds are improved.In addition, cover layer and metal forming are all conductors, so molecular separating force is relatively good.For above-mentioned reason, the electrode that interface Strong degree improves can be obtained in the present embodiment, and without the need to mixed polymer in cover layer.
Note, when to when using the situation of not carried out the modification of polymer by the collector of the cover layer covering metal paper tinsel of mixed polymer and present embodiment to compare, known, by adopting present embodiment, the bonding Strong degree at metal forming and tectal interface can be improved, and can be implemented in its entirety the electrode not easily occurring to peel off.
Above-mentioned situation can to illustrate as follows.When using the cover layer of mixing carbon particle and polymer, the high molecular molecular separating force with Kynoar structure in polymer in cover layer and active material layer becomes greatly, so the interface Strong degree of cover layer and active material layer is improved compared with present embodiment.On the other hand, the bonding Strong degree of cover layer and metal forming depends on the cohesive force of oxide skin(coating) and polymer, so this bonding Strong degree dies down compared with present embodiment.That is, can say that bonding Strong degree and the cover layer of cover layer and metal forming are more remarkable than present embodiment with the difference of the bonding Strong degree of active material layer.Therefore, can think: when applying to electrode strength collector and active material layer will peeled off, this peeling force concentrates between cover layer and active material layer.
Compared with the above case, by adopting present embodiment, electrode Strong degree can be improved.Note, as the reason of bonding Strong degree improving cover layer and active material layer, herein illustrating the molecular separating force produced between the carbon particle be contained in cover layer and the macromolecule be contained in active material layer, but in conjunction with this reason can also be counted as, be namely contained in the carbon particle in cover layer and the high molecular polymerization being contained in the modification in active material layer.
By above-mentioned steps, the storage battery electrode of the high molecular active material layer comprising metal forming, the layer (cover layer) be made up of carbon particle in fact and comprise the Kynoar structure with modification can be manufactured.
Present embodiment can suitably combine with other execution modes and implement.
Execution mode 3
In the present embodiment, other manufacture methods of the storage battery electrode illustrated by execution mode 1 are explained.
First, carry out mixingly modulating paste mixture to graphene oxide, active material particle and polar solvent.Then, paste mixture is carried out dry thick mixing (mixing with high viscosity).When mixing with high viscosity, easily produce Strong shear power, so graphene oxide can be made to peel off and make graphene oxide or active material particle disperse equably.Especially when using containing the material of aerobic as active material 103, active material particle and graphene oxide can be made to disperse equably, and can be little at aggregate particle size, namely in gathering by mixing under the state removed.
Obtained paste mixture is carried out dry thick mixing.At this, dry thick mixing refer to high viscosity carry out mixing.Dry thick mixing and produce larger shearing force by carrying out, therefore easily there is active material or the dispersion of graphene oxide and the stripping of graphene oxide.As carrying out dry thick mixing method, the device such as planetary mixer or kneader can be used.
Also solvent can be added further to the mixture of dispersion.Generally speaking, more low being more not easy of concentration is polymerized again, therefore more easily makes aggregate particle size diminish.
Then, obtained mixture is reacted in the solution comprising reducing agent.By this reaction, make the graphene oxide reduction be contained in mixture, and form Graphene.Note, the oxygen be included in graphene oxide is not necessarily all released, and a part for oxygen also can remain in Graphene.When Graphene is containing aerobic, the ratio of the oxygen measured by XPS is more than the 1atm% of Graphene entirety and below 20atm%, is preferably more than 2atm% and below 15atm%.This reduction treatment preferably more than room temperature and less than 150 DEG C carry out.This reduction can add the laggard row of hot mixt, directly can also add reducing solution to the mixture of pulp-like or paste.When carrying out this reduction after the heating, this heating process causes gathering, but can become graphene oxide and be attached to aggregate particles on the active material offspring of minimum (assemble and removed).By selecting compounding conditions, such as can be attached to by the mixing graphene oxide that obtains the particle that diameter is each primary particle of below 100nm, the aggregate particles that therefore can be obtained by heating can be in the state that each primary particle contacts with graphene oxide.This aggregate particles has fabulous conductive path in cell reaction, therefore easily presents good battery behavior.The difficulty of particle coating depends on the particle diameter of offspring, and namely the particulate of less than several microns is not easy coating, therefore by utilizing aggregate particles can overcome this shortcoming.By this process, graphene oxide becomes RGO.
As solute, can use and there is more than-5.0eV and the material of lumo energy below-3.8eV.Or, can use and there is more than-1.3V and (vs.SCE) below+0.8V, be preferably more than-0.4V and the reducing agent of the reduction potential of (vs.SCE) below+0.8V.As concrete reducing agent, ascorbic acid, hydrazine, dimethylhydrazine, hydroquinones, sodium borohydride (NaBH can be enumerated
4), TBAB (TBAB), N, N-diethyl hydroxylamine and their derivative.Especially when the reducing agent using reducing power more weak, just not on the impact of active material.In addition, be not easy react with the moisture in solvent or air and decompose, so tail off to the restriction that reduction treatment environment or solvent are selected.
Polar solvent can be used as solvent.As long as the solvent that reducing agent can be made to dissolve just not limiting material.Such as, the mixed liquor of any one or more in water, methyl alcohol, ethanol, acetone, THF, DMF, NMP and DMSO can be used.Especially, when using water, industrial advantage is larger.In addition, by using water, can Reaction time shorten.
Then, the particle obtained is collected.Meanwhile also can wash.The solvent of reducing solution can be used as cleaning solution.By washing, the reducing agent stayed can be removed.Further, can also promote to depart from reaction in RGO.Especially, when using pure water, easily promoting the disengaging reaction in RGO, and there is larger industrial advantage, so be preferred.Centrifugation or filtration etc. can be used when collecting.
Collected particle is heated, removes the solvent stayed.This heating also can double as the thermal reduction of RGO, can be referred to as heat treated.Heat treated can be carried out under vacuum atmosphere, air atmosphere or inert atmosphere.Evaporator etc. can also be used.Also multiple heating condition can be combined.Heat treated can carried out at the temperature of about 800 DEG C from room temperature.Also make that the oxygen in RGO departs from further at higher temperatures and conductance is improved, so be preferred, and, heat treated can be carried out in the Undec scope of active material.
Adhesive and solvent adjustment viscosity are added to the stuff and other stuff of obtained active material and RGO, forms pulp-like mixture.Carry out mixing means as to pulp-like mixture, can use and stir the various mixer such as defoamer or homogenizer.
At this, use the macromolecule with Kynoar structure as adhesive.As the macromolecule with Kynoar structure, can enumerate PVdF, comprise the copolymer of PVdF, such as, be the copolymer of PVdF and PTFE.PVdF is once react with alkali, and hydrofluoric disengaging reaction just occurs chainly.By using copolymer, this chain reaction can be suppressed.
Moisture is added to pulp-like mixture.By the modification of this process generation Kynoar structure, namely there is hydrofluoric disengaging.That is, a part for Kynoar structure becomes polyene structure or cyclisation and becomes aromatic ring structure.Again can not add moisture in this process, and utilize the moisture that the solvent that uses in the manufacturing process of slurry comprises, when also can utilize mixing or mixing after work atmosphere in moisture.Note, if the modification of PVdF is excessive, then cause the decline of high molecular gelation or adhesive function, therefore preferably only make a part of modification of PVdF.That is, a part of modification of continuous print Kynoar structure is preferably only made.Now, can say that produced polyene structure or aromatic ring structure are clipped between Kynoar structure.
After fully making adhesive modification, pulp-like mixture is coated on a face or two-sided of collector.As coating method, such as, can use slit fashion of extrusion, intaglio plate mode, scraper mode and combine the method for these modes.
Then, adopt the method such as aeration-drying or drying under reduced pressure to make the solvent evaporates being contained in mixture, form the electrode comprising active material layer 102 and collector.Aeration-drying such as can use more than 50 DEG C and the hot blast of less than 180 DEG C.Thus, the polar solvent volatilization be included in active material layer 102 is made.
Note, the content of the graphene oxide of raw material is preferably more than the 0.1wt% of the mixture total weight amount of graphene oxide, positive active material, conductive auxiliary agent and binding agent and below 10wt%, be preferably more than 0.1wt% and below 5wt%, be more preferably more than 0.2wt% and below 2wt%, more preferably more than 0.2wt% and below 1wt%.On the other hand, the content of Graphene is more than the 0.05wt% of the total weight of active material layer and below 5wt% in the electrodes, be preferably more than 0.05wt% and below 2.5wt%, be more preferably more than 0.1wt% and below 1wt%, more preferably more than 0.1wt% and below 0.5wt%.This is because the weight of Graphene approximately reduces half due to the reduction of graphene oxide.The content of adhesive is more than 0.5wt% and below 20wt%, is preferably more than 1wt% and below 10wt%.
Roll-in method or the isobaric compression method of dull and stereotyped platen press is preferably utilized to press this active material layer and make its densification.
By above-mentioned steps, can manufacture comprise the Kynoar structure with modification macromolecule, Graphene, active material particle storage battery electrode 100.
Present embodiment can suitably combine with other execution modes and implement.
Execution mode 4
In the present embodiment, the structure of the storage battery using the storage battery electrode manufactured by the manufacture method shown in execution mode 1 is described with reference to Fig. 4 A to Fig. 7 B.
(Coin shape storage battery)
Fig. 4 A is the outside drawing of Coin shape (simple squamous type) storage battery, and Fig. 4 B is its sectional view.
In Coin shape storage battery 300, double as the positive pole tank (positiveelectrodecan) 301 of positive terminal and double as the cathode pot (negativeelectrodecan) 302 of negative terminal by pad 303 insulated enclosure formed by polypropylene etc.Positive pole 304 is formed by plus plate current-collecting body 305 with the positive electrode active material layer 306 that the mode be in contact with it is arranged.In addition, negative pole 307 is formed by negative current collector 308 with the negative electrode active material layer 309 that the mode be in contact with it is arranged.Barrier film 310 and electrolyte (not shown) is comprised between positive electrode active material layer 306 and negative electrode active material layer 309.
The storage battery electrode of the manufacture method manufacture by the storage battery electrode according to a mode of the present invention shown in execution mode 1 can be used as positive pole 304 and negative pole 307.
As barrier film 310, insulator such as cellulose (paper), polypropylene or the polyethylene etc. with emptying aperture can be used.
As electrolyte, except solid electrolyte, comprise supporting electrolyte electrolyte except, the gel electrolyte of a part of gelation of electrolyte can also be used.
As supporting electrolyte, the material with carrier ion can be used.As the exemplary of supporting electrolyte, LiPF can be enumerated
6, LiClO
4, LiAsF
6, LiBF
4, LiCF
3sO
3, Li (CF
3sO
2)
2n, Li (C
2f
5sO
2)
2the lithium salts such as N.These electrolyte both can be used alone, again can by two or more to combine arbitrarily and ratio use.
In addition, when carrier ion is alkali metal ion, alkaline-earth metal ions beyond lithium ion, also can use alkali metal (such as, sodium, potassium) as electrolyte, lithium that alkaline-earth metal (such as, calcium, strontium, barium, beryllium or magnesium) replaces in above-mentioned lithium salts.
In addition, as the solvent of electrolyte, can use carrier ion can the material of movement.As the solvent of electrolyte, preferably use non-proton organic solvent.As the exemplary of non-proton organic solvent, can use in ethylene carbonate (EC), propylene carbonate, dimethyl carbonate, diethyl carbonate (DEC), gamma-butyrolacton, acetonitrile, glycol dimethyl ether, THF etc. one or more.In addition, when the solvent as electrolyte uses the macromolecular material of gelation, the fail safe of anti-leakage etc. is improved.Further, slimming and the lightweight of storage battery can be realized.As the exemplary of the macromolecular material of gelation, silicone adhesive, acrylate glue, acrylonitrile glue, polyethylene glycol oxide class glue, PPOX class glue, fluorine-based polymer class glue etc. can be enumerated.In addition, by using one or more as the solvent of electrolyte, there is anti-flammability and difficult volatile ionic liquid (especially room temperature molten salt), even if make internal temperature rise due to the internal short-circuit, overcharge etc. of storage battery, also can prevent storage battery break or on fire etc.Ionic liquid is made up of cation and anion.As the organic cation forming ionic liquid, quaternary ammonium cation, tertiary sulfonium cation can be enumerated Ji aliphat cation or the aromatic series such as glyoxaline cation and pyridylium cations such as quaternary phosphine cations.In addition, monovalence amide-type anion, monovalence methide anionoid, fluosulfonic acid anion, perfluoro alkyl sulfonic acid anion, tetrafluoroborate, perfluoroalkyl borate, hexafluorophosphate or perfluoroalkyl phosphate can be enumerated as the anion for electrolyte.
In addition, can use there is the inorganic material such as sulfide-based or oxide-based solid electrolyte, there is the solid electrolyte of the macromolecular materials such as PEO (poly(ethylene oxide)) class to replace electrolyte.When using solid electrolyte, do not need to arrange barrier film or sept.In addition, can make cell integrated solidification, so do not have the worry of leakage, fail safe is significantly improved.
Positive pole tank 301 and cathode pot 302 can be used in the discharge and recharge of secondary cell has the alloy of metal, the alloy of above-mentioned metal, above-mentioned metal and other metals such as nickel, aluminium, titanium of corrosion stability (such as to liquid such as electrolyte, stainless steel etc.), the lamination of the lamination of above-mentioned metal, above-mentioned metal and described alloy (such as, stainless steel/aluminium etc.), the lamination (such as, nickel/iron/nickel etc.) of above-mentioned metal and other metals.Positive pole tank 301 is electrically connected with positive pole 304, and cathode pot 302 is electrically connected with negative pole 307.
These negative poles 307, positive pole 304 and barrier film 310 be impregnated in electrolyte, as shown in Figure 4 B, positive pole tank 301 is arranged on below, stack gradually positive pole 304, barrier film 310, negative pole 307, cathode pot 302, make pad 303 between positive pole tank 301 and cathode pot 302 and carry out pressing, manufacturing Coin shape storage battery 300 thus.
(laminated-type storage battery)
Fig. 5 illustrates the outside drawing of laminated-type storage battery 500.In addition, Fig. 6 A and Fig. 6 B illustrates the A1-A2 cross section represented with chain-dotted line and the B1-B2 cross section of Fig. 5.Laminated-type storage battery 500 comprises: the positive pole 503 comprising plus plate current-collecting body 501 and positive electrode active material layer 502; Comprise the negative pole 506 of negative current collector 504 and negative electrode active material layer 505; Barrier film 507; Electrolyte 508; And external packing body 509.Barrier film 507 is provided with between the positive pole 503 be arranged in external packing body 509 and negative pole 506.In addition, by external packing body 509 around region in be injected into electrolyte 508.
In the laminated-type storage battery 500 shown in Fig. 5, plus plate current-collecting body 501 and negative current collector 504 are also used as the terminal with external electrical contact.Therefore, a part for plus plate current-collecting body 501 and negative current collector 504 is exposed to the outside of external packing body 509.
In laminated-type storage battery 500, as external packing body 509, such as can use the laminated film of following three-decker: the metallic film that the high flexibilities such as aluminium, stainless steel, copper, nickel are set on the film be made up of the material of polyethylene, polypropylene, Merlon, ionomer, polyamide etc., and on this metallic film, the insulative synthetic resin such as polyamide-based resin, polyester resin film is set as the outer surface of external packing body.By adopting above-mentioned three-decker, can blocking electrolyte and gas through while guarantee insulating properties, and there is electrolyte resistance.
(cylinder type storage battery)
Next, with reference to Fig. 7 A and Fig. 7 B, cylinder type storage battery example is described.As shown in Figure 7 A, cylinder type storage battery 600 has positive cover (battery cover) 601 at end face, and has battery can (outer tinning) 602 in side and bottom surface.Pad (insulation spacer) 610 makes above-mentioned positive cover 601 insulate with battery can (outer tinning) 602.
Fig. 7 B is the figure in the cross section schematically showing cylinder type storage battery.The inner side of hollow cylindrical battery can 602 is provided with cell device, and in this cell device, banded positive pole 604 and banded negative pole 606 clip barrier film 605 and are wound.Although not shown, cell device is wound centered by centrepin.One end of battery can 602 closes and the other end opens.Battery can 602 can be used in the discharge and recharge of secondary cell has the alloy of metal, the alloy of above-mentioned metal, above-mentioned metal and other metals such as nickel, aluminium, titanium of corrosion stability (such as to liquid such as electrolyte, stainless steel etc.), the lamination of the lamination of above-mentioned metal, above-mentioned metal and described alloy (such as, stainless steel/aluminium etc.), the lamination (such as, nickel/iron/nickel etc.) of above-mentioned metal and other metals.In the inner side of battery can 602, the cell device that positive pole, negative pole and barrier film are wound is clipped by opposed a pair insulation board 608,609.In addition, in the inside of battery can 602 being provided with cell device, nonaqueous electrolytic solution (not shown) is injected with.As nonaqueous electrolytic solution, the electrolyte identical with Coin shape or laminated-type storage battery can be used.
Positive pole 604 and negative pole 606 is manufactured in the same manner as the positive pole of above-mentioned Coin shape storage battery and negative pole, but the difference of itself and Coin shape storage battery is: because be wound, so active material is formed in two faces of collector for the positive pole of cylinder type storage battery and negative pole.Positive pole 604 is connected with positive terminal (positive pole current collection wire) 603, and negative pole 606 is connected with negative terminal (negative pole current collection wire) 607.Positive terminal 603 and negative terminal 607 can use the metal materials such as aluminium.By positive terminal 603 resistance welded to relief valve mechanism 612, and by negative terminal 607 resistance welded to battery can 602 end.Relief valve mechanism 612 is electrically connected by PTC (PositiveTemperatureCoefficient: positive temperature coefficient) element 611 with positive cover 601.When pressure in battery rises above the threshold value of specifying, relief valve mechanism 612 cuts off the electrical connection of positive cover 601 and positive pole 604.In addition, PTC element 611 is thermistor elements that its resistance increases when temperature rises, and carrys out Limited Current amount to prevent abnormal heating by the increase of resistance.As PTC element, barium titanate (BaTiO can be used
3) based semiconductor pottery etc.
In the present embodiment, although illustrate the storage battery of Coin shape, laminated-type and cylinder type as storage battery, other storage batterys of the various shape such as enclosed type accumulators, square storage battery can be used.In addition, also can adopt be laminated with multiple positive pole, multiple negative pole, multiple barrier film structure and be wound with the structure of positive pole, negative pole, barrier film.
As the negative or positive electrode of the storage battery 300 shown in present embodiment, storage battery 500, storage battery 600, the electrode manufactured by the manufacture method of the storage battery electrode of a mode according to the present invention can be used.Therefore, the discharge capacity of storage battery 300, storage battery 500, storage battery 600 can be improved.
Present embodiment can suitably combine with other execution modes and implement.
Execution mode 5
Use and can be used as with the power supply of power-actuated various electronic equipment according to the storage battery of the storage battery electrode of a mode of the present invention.
As comprising the object lesson used according to the electronic equipment of the storage battery of the storage battery electrode of a mode of the present invention, television set can be enumerated, the display unit such as display, lighting device, desk-top or notebook-sized personal computer, word processor, reproduction is stored in the image-reproducing means of still image in the recording mediums such as DVD (DigitalVersatileDisc: digital versatile disc) or dynamic image, portable CD player, broadcast receiver, tape recorder, headphone, sound equipment, table clock, wall clock, Subset of cordless telephone, walkie-talkie, mobile phone, car phone, portable game machine, calculator, portable data assistance, electronic memo, E-book reader, electronic interpreter, Speech input device, video camera, digital still camera, toy, electric shaver, the thermatrons such as microwave oven, electric cooker, washing machine, dust catcher, water heater, electric fan, hair dryer, air-conditioning equipment is air conditioner such as, humidifier and dehumidifier, dishwasher, dish drier, dryer, quilt dryer, refrigerator, electricity household freezer, electricity household refrigerator-freezer, DNA preserves and uses freezing device, flashlight, the electric tools such as chain saw, smoke detector, the Medical Devices etc. such as dialysis apparatus.Moreover, can also enumerate industrial equipment such as guiding lamp, semaphore, conveyer belt, escalator, elevator, industrial robot, accumulating system, for making the electrical storage device etc. of electric power homogenizing or intelligent grid.In addition, the moving body etc. utilizing the electric power from storage battery to be advanced by motor is also included within the category of electronic equipment.As above-mentioned moving body, such as can enumerate electric automobile (EV), have the hybrid vehicle (HEV) of internal combustion engine and motor concurrently, plug-in hybrid-power automobile (PHEV), use that crawler belt replaces the caterpillar of these wheel, comprises the bicycle with engine of electrically assisted bicycle, motorcycle, electric wheelchair, golf cart, small-sized or large ship, submarine, helicopter, aircraft, rocket, artificial satellite, space probe, planetary probe, spaceship etc.
In addition, in above-mentioned electronic equipment, as the main power source being used for supplying roughly whole power consumption, the storage battery of the storage battery electrode had according to a mode of the present invention can be used.Or, in above-mentioned electronic equipment, as the uninterrupted power supply can supplying electric power when the supply of electric power from above-mentioned main power source or commercial power stops to electronic equipment, the storage battery of the storage battery electrode had according to a mode of the present invention can be used.Or, in above-mentioned electronic equipment, supply power to the accessory power supply of electronic equipment as with above-mentioned main power source or commercial power simultaneously, the storage battery of the storage battery electrode had according to a mode of the present invention can be used.
Fig. 8 illustrates the concrete structure of above-mentioned electronic equipment.In fig. 8, display unit 700 comprises the example used according to the electronic equipment of the storage battery 704 of the storage battery electrode of a mode of the present invention.Specifically, display unit 700 is equivalent to broadcast TV reception display unit, comprises framework 701, display part 702, loud speaker portion 703 and storage battery 704 etc.Use the inside being arranged on framework 701 according to the storage battery 704 of the storage battery electrode of a mode of the present invention.Display unit 700 both can receive the supply of electric power from commercial power, can use again the electric power be accumulated in storage battery 704.Therefore, even if when the supply of electric power from commercial power can not be received due to power failure etc., by the storage battery 704 used according to the storage battery electrode of a mode of the present invention is used as uninterrupted power supply, also display unit 700 can be utilized.
As display part 702, the semiconductor display devices such as such as liquid crystal indicator, the light-emitting device possessing the light-emitting components such as organic EL element in each pixel, electrophoretic display apparatus, DMD (digital micro-mirror device: DigitalMicromirrorDevice), PDP (plasma display: PlasmaDisplayPanel) and FED (field-emitter display: FieldEmissionDisplay) can be used.
In addition, except broadcast TV reception is used, the display unit for all information displaying of personal computer or advertisement display etc. comprises in a display device.
In fig. 8, pacifying edge type lighting device 710 is comprise the example used according to the electronic equipment of the storage battery 713 of the storage battery electrode of a mode of the present invention.Specifically, lighting device 710 comprises framework 711, light source 712 and storage battery 713 etc.Although exemplify the situation that storage battery 713 is arranged on the inside of the ceiling 714 studding with framework 711 and light source 712 in fig. 8, storage battery 713 also can be arranged on the inside of framework 711.Lighting device 710 both can receive the supply of electric power from commercial power, can use again the electric power be accumulated in storage battery 713.Therefore, even if when the supply of electric power from commercial power can not be received due to power failure etc., by the storage battery 713 used according to the storage battery electrode of a mode of the present invention is used as uninterrupted power supply, also lighting device 710 can be utilized.
In addition, although exemplify the peace edge type lighting device 710 being arranged on ceiling 714 in fig. 8, but use the peace edge type lighting device that both may be used for being arranged on such as sidewall 715 beyond ceiling 714, floor 716 or window 717 etc. according to the storage battery of the storage battery electrode of a mode of the present invention, may be used for desk-top lighting device etc. again.
In addition, for light source 712, obtain light artificial light source with utilizing the artificial property of electric power can be used.Specifically, as an example of above-mentioned artificial light source, the discharge lamp such as incandescent lamp bulb, fluorescent lamp and the light-emitting component such as LED or organic EL element can be enumerated.
In fig. 8, the air conditioner with indoor set 720 and off-premises station 724 comprises the example used according to the electronic equipment of the storage battery 723 of the storage battery electrode of a mode of the present invention.Specifically, indoor set 720 comprises framework 721, air outlet 722 and storage battery 723 etc.Although exemplify the situation in storage battery 723 machine 720 disposed in the interior in fig. 8, storage battery 723 also can in machine 724 disposed in the outdoor.Or, also can be provided with storage battery 723 in the both sides of indoor set 720 and off-premises station 724.Air conditioner both can receive the supply of electric power from commercial power, can use again the electric power be accumulated in storage battery 723.Especially, when being provided with storage battery 723 in the both sides at indoor set 720 and off-premises station 724, even if when the supply of electric power from commercial power can not be received due to power failure etc., by the storage battery 723 used according to the storage battery electrode of a mode of the present invention is used as uninterrupted power supply, also air conditioner can be utilized.
In addition, although exemplify the detachable air conditioner be made up of indoor set and off-premises station in fig. 8, also use can be used for the integral air conditioner in a framework with the function of indoor set and the function of off-premises station according to the storage battery of the storage battery electrode of a mode of the present invention.
In fig. 8, electric household refrigerator-freezer 730 comprises the example used according to the electronic equipment of the storage battery 734 of the storage battery electrode of a mode of the present invention.Specifically, electric household refrigerator-freezer 730 comprises framework 731, refrigerating-chamber door 732, refrigerating chamber door 733 and storage battery 734 etc.In fig. 8, storage battery 734 is arranged on the inside of framework 731.Electricity household refrigerator-freezer 730 both can receive the supply of electric power from commercial power, can use again the electric power be accumulated in storage battery 734.Therefore, even if when the supply of electric power from commercial power can not be received due to power failure etc., by the storage battery 734 used according to the storage battery electrode of a mode of the present invention is used as uninterrupted power supply, electric household refrigerator-freezer 730 also can be utilized.
In addition, in above-mentioned electronic equipment, the electronic equipments such as thermatron and electric cooker such as microwave oven need high electric power at short notice.Therefore, by by using according to the storage battery of the storage battery electrode of a mode of the present invention as being used for the accessory power supply of electric power that auxiliary commerce power supply supplies not, can prevent the master switch of commercial power from tripping when using electronic equipment.
In addition, do not using the time period of electronic equipment, especially in the time period that the ratio (being called electricity usage rate) of the actual electricity used is low in total electricity that the source of supply of commercial power can be supplied, electric power is accumulated in storage battery, electricity usage rate in the time period beyond the above-mentioned time period can be suppressed thus to increase.Such as, when adopting electric household refrigerator-freezer 730, low and do not carry out night of the switch of refrigerating-chamber door 732 or refrigerating chamber door 733 at temperature, electric power is accumulated in storage battery 734.Further, high and carry out daytime of the switch of refrigerating-chamber door 732 or refrigerating chamber door 733 at temperature, storage battery 734 is used as accessory power supply, the electricity usage rate on daytime can be suppressed thus.
Present embodiment can suitably combine with other execution modes and implement.
Execution mode 6
Then, use Fig. 9 A to Fig. 9 C that the portable data assistance of an example of electronic equipment is described.
Fig. 9 A and Fig. 9 B illustrates the tablet terminal 800 can carrying out folding.Fig. 9 A is the state opened, and tablet terminal 800 comprises framework 801, display part 802a, display part 802b, display mode diverter switch 803, mains switch 804, battery saving mode diverter switch 805 and console switch 807.
In display part 802a, its part can be used as the region 808a of touch-screen, and can by inputting data by touching shown operation keys 809.In addition, as an example, illustrate that the half of display part 802a only has the function of display and second half has the structure of the function of touch-screen, but be not limited to this structure.Also the structure making the whole region of display part 802a have the function of touch-screen can be adopted.Such as, whole the display keyboard button of display part 802a can be made to come used as touch-screen, and display part 802b is used as display screen.
In addition, the region 808b that also a part of display part 802b can be used as touch-screen same with display part 802a in display part 802b.In addition, by using finger or screen touch pen etc. by the position of the keyboard & display switching push button 810 touched on touch-screen, can on display part 802b display keyboard button.
In addition, also can carry out touch input to the region 808b of the region 808a of touch-screen and touch-screen simultaneously.
In addition, display mode diverter switch 803 diverter shaft screen display can be shown the direction of displays such as showing with horizontal screen display and selects the switching of white and black displays or colored display etc.The light quantity of the outer light during use of arriving according to the light sensors built-in by tablet terminal, the brightness settings of display can be optimal brightness by battery saving mode diverter switch 805.Tablet terminal all right built-in gyroscope and acceleration transducer etc. except optical sensor detect other checkout gears of the sensor of gradient.
In addition, Fig. 9 A illustrates the example that the display area of display part 802b is identical with the display area of display part 802a, but is not limited to this, and the size of a side not only can have been made different with the size of the opposing party but also their display quality can be made variant.Such as display part 802a and the side in display part 802b can carry out the display of fine compared with the opposing party.
Fig. 9 B is the state of closing, and tablet terminal 800 comprises framework 801, solar cell 811, charge-discharge control circuit 850, battery 851 and DC-DC converter 852.In addition, in figures 9 b and 9, an example as charge-discharge control circuit 850 illustrates the structure with battery 851 and DC-DC converter 852, and battery 851 has use illustrated by above-mentioned execution mode according to the storage battery of the storage battery electrode of a mode of the present invention.
In addition, tablet terminal 800 can fold, so framework 801 of can closing when not using.Therefore, display part 802a and display part 802b can be protected, and can provide a kind of and there is good durability and there is from the viewpoint of Long-Time Service the tablet terminal 800 of good reliability.
In addition, Fig. 9 A and the tablet terminal shown in Fig. 9 B can also have: the function showing various information (still image, dynamic image, character image etc.); Calendar, date or moment etc. are presented at the function on display part; The information be presented on display part is carried out to the touch-input function of touch input operation or editor; By the function of various software (program) control treatment; Deng.
By utilizing the solar cell 811 being installed on the surface of tablet terminal, touch-screen, display part or picture signal handling part etc. can be supplied power to.In addition, can solar cell 811 be arranged on the single or double of framework 801, can charge efficiently to battery 851 thus.
In addition, the block diagram shown in Fig. 9 C is used to be described the structure of the charge-discharge control circuit 850 shown in Fig. 9 B and work.Fig. 9 C illustrates solar cell 811, battery 851, DC-DC converter 852, transducer 853, interrupteur SW 1 to interrupteur SW 3 and display part 802, battery 851, DC-DC converter 852, transducer 853, the charge-discharge control circuit 850 shown in interrupteur SW 1 to interrupteur SW 3 corresponding diagram 9B.
First, the example of the work when utilizing outer light to make solar cell 811 generate electricity is described.The electric power using DC-DC converter 852 pairs of solar cells to produce boost or step-down to become the voltage for charging to battery 851.Further, when utilizing and making display part 802 work from the electric power of solar cell 811, interrupteur SW 1 is connected, and, utilize transducer 853 to be boosted or be depressured to the voltage required for display part 802.In addition, when not carrying out the display in display part 802, can adopt and interrupteur SW 1 is disconnected and makes interrupteur SW 2 connect the structure of charging to battery 851.
In addition, an example as generator unit illustrates solar cell 811, but be not limited to this, other generator units such as piezoelectric element (piezoelectricelement) or thermoelectric conversion element (Peltier's element (Peltierelement)) also can be used to carry out the charging of battery 851.Such as, also can use can receive and dispatch electric power to carry out the wireless power transmission module of charging in the mode of wireless (not contacting) or combine other charging methods and charge.
Certainly, as long as the use possessed illustrated by above-mentioned execution mode is according to the storage battery of the storage battery electrode of a mode of the present invention, the electronic equipment shown in Fig. 9 A to Fig. 9 C is just not limited to.
Execution mode 7
Moreover, use Figure 10 A and Figure 10 B that the example of the moving body of an example of electronic equipment is described.
Storage battery illustrated by above-mentioned execution mode can be used for control battery.Can charge to control battery from outside supply electric power by utilizing plug-in technology or non-contact power.In addition, when moving body is railways motor-car railway carriage or compartment, can charge from aerial cable or conductor rail supply electric power.
Figure 10 A and Figure 10 B illustrates an example of electric automobile.Battery 861 is installed in electric automobile 860.The electric power of battery 861 is adjusted by control circuit 862, and is fed to drive unit 863.Control circuit 862 is controlled by the processing unit 864 comprising not shown ROM, RAM, CPU etc.
Drive unit 863 is made up of the combination of single DC motor, single alternating current motor or motor and internal combustion engine.Processing unit 864, according to input information such as the operation information (acceleration, deceleration, stopping etc.) of the driver of electric automobile 860 or running informations information such as () loads that the wheel in the information such as climbing, descending or driving is subject to, exports control signal to control circuit 862.The output of the controlling electric energy drive unit 863 that control circuit 862 utilizes the control signal adjustment of processing unit 864 to supply from battery 861.When being provided with alternating current motor, although not shown, be also built-in with inverter direct current being converted to interchange.
Can charge to battery 861 from outside supply electric power by utilizing plug-in technology.Such as, charged to battery 861 from commercial power by attaching plug.The DC constant voltage with fixed voltage value can be converted to by conversion equipments such as AC/DC transducers to charge.By installing and using according to the storage battery of the storage battery electrode of the present invention's mode as battery 861, contributing to the high capacity of battery etc. and can convenience be improved.In addition, when can be realized the miniaturization and of battery 861 itself by the characteristic improving battery 861, vehicle lightweight can be made, so power consumption can be reduced.
Certainly, as long as possess the storage battery of a mode of the present invention, above-mentioned electronic equipment is just not limited to.
Present embodiment can suitably combine with other execution modes and implement.
Embodiment 1
Below, embodiment is used to further illustrate a mode of the present invention.Note, a mode of the present invention is not confined to following examples.
< material and device >
Below, the material that the present embodiment uses and device are shown.
As graphite, employ the BF-40AK of Yueshi ink manufactured by industrial group in Japan.As lithium carbonate Li
2cO
3(99.99%, anhydrous), employs the material bought from Japanese high-purity chemical research institute.As ammonium dihydrogen phosphate NH
4h
2pO
4(99%) and D (+)-glucose (98%, hereinafter referred to as glucose), the material bought from Japanese KISHIDA chemical company (KishidaChemicalCo., Ltd.) is employed.As ferric oxalate FeC
2o
42H
2o (98%, dihydrate), employs the material bought from Japanese KISHIDA chemical company.As L-AA (99.6%, hereinafter referred to as ascorbic acid), employ the material bought from Japan and Guang Chun medicine industrial group.As PVdF, employ 7300 (the 5wt%NMP solution) that Japanese Wu Yu company manufactures.As plus plate current-collecting body, employ the aluminium foil covered by the layer be made up of carbon black in fact.As with reference to plus plate current-collecting body, employ by applying the carbon black dispersion and capped aluminium foil that comprise polymer.As negative current collector, employ rolled copper foil.As the LiPF containing 1M
6the mixed solvent (EC:DEC=1vol:1vol, LITHIUM BATTERY) of ethylene carbonate (EC) and diethyl carbonate (DEC), employ the material bought from Japanese KISHIDA chemical company.
The small spraying drying instrument B-290 manufactured by Japanese BUCHI company is employed in spraying dry.When adhesive tape 180 ° of disbonded tests, employ the EZGraph that Shimadzu Corp manufactures.When measuring electrode resistance, employ resistance analysis (Loresta) GP that Mitsubishi chemical analysis technology company (MitsubishiChemicalAnalytechCo., Ltd.) manufactures and the PSP type probe that the said firm manufactures.
The synthesis > of < graphene oxide
Synthesize graphene oxide in the following manner.First, while the potassium permanganate of 75g is slowly added on the concentrated sulfuric acid limit of the graphite and 690mL (96%) that stir 20g under ice bath.Then, stir 4.5 hours with 25 DEG C and obtain reactant liquor 1.Then, under ice bath, reactant liquor 1 slowly added to the pure water of 1380mL and dilute.Then, with ca.95 DEG C, diluted reactant liquor 1 is stirred 15 minutes under oil bath and after reacting, the aquae hydrogenii dioxidi (concentration is 30wt%) adding 54mL under water-bath (room temperature) makes unreacted potassium permanganate inactivation.Collecting after solid through centrifugation, carry out washing and drying to obtain graphene oxide powder.At this, wash and carry out through the operation of centrifugation collecting precipitation thing after repeated multiple times carrying out diluting at interpolation pure water, disperseing.In addition, spraying dry instrument is used when carrying out drying.
< active material particle LiFePO
4synthesis >
To Li
2cO
3, FeC
2o
42H
2o, NH
4h
2pO
4(mol ratio is 1:2:2) adds acetone (dehydration), uses medium stirring mill machine (mediumstirringmill) to carry out pulverizing and mixing.After making to be contained in the solvent evaporates in mixture, obtain material 1 with 350 DEG C of roastings 10 hours under nitrogen atmosphere.Then, glucose (weight ratio for material 1 is 10wt%) and acetone are added to material 1, use medium wet milk (wetmediummill) to mix, make solvent evaporates to obtain material 2.With 600 DEG C, roasting is carried out to material 2 under nitrogen atmosphere and obtain material 3 in 10 hours.Use acetone and utilize medium wet milk to make material 3 micronize, by its dispersion, and making solvent evaporates to obtain material 4.This material 4 is used as active material particle LiFePO
4.Note, by the parsing of XRD, the crystallite size of known material 4 is ca.80nm, and specific area is 27m
2/ g.
Figure 11 A and Figure 11 B illustrates the particle size distribution of the active material particle measured in aqueous solvent.Figure 11 A illustrates frequency distribution, and Figure 11 B illustrates cumulative distribution.90% particle diameter (particle diameter when cumulant is 90% in cumulative distribution) is 2.708 μm.
The manufacture > of < electrode
To active material particle LiFePO
4, graphene oxide, PVdF solution add NMP, and use the rotary-type homogenizer of film come mixing.The weight ratio removing the material of solvent NMP is LiFePO
4: graphene oxide: PVdF=94.2:0.8:5.0.To scrape the skill in using a kitchen knife in cookery, obtained pulp-like mixture is coated on plus plate current-collecting body, carries out heated-air drying with the temperature of 65 DEG C to 75 DEG C, obtain the electrode 1 comprising positive electrode active material layer.In addition, active material particle LiFePO will be comprised to scrape the skill in using a kitchen knife in cookery
4, graphene oxide, PVdF the pulp-like mixture of nmp solution be coated on reference on plus plate current-collecting body, carry out heated-air drying to obtain the electrode 2 comprising positive electrode active material layer.The mixing ratio of electrode 2 is identical with electrode 1.
Electrode 1 is soaked in the nmp solution of the lithium hydroxide of the ascorbic acid of the water comprising 10vol%, 77mM, 75mM, and make it react 1 hour with 60 DEG C.Then, ethanol is used to wash several times reacted electrode 1 (hereinafter referred to as electrode 1a).Drying is carried out to the electrode 1a after washing, and carries out the heat treated of 10 hours with 170 DEG C under vacuo.Electrode 1a after heat treated is pressed, obtains electrode A thus.Electrode A is struck out the circle of diameter 12mm, used as positive pole A.
Electrode 1 is soaked in the nmp solution of the lithium hydroxide of the ascorbic acid of the water comprising 10vol%, 77mM, 75mM, and make it react 1 hour with 60 DEG C.Then, pure water is used to wash several times reacted electrode 1 (hereinafter referred to as electrode 1b).Drying is carried out to the electrode 1b after washing, and carries out the heat treated of 10 hours with 170 DEG C under vacuo.Electrode 1b after heat treated is pressed, obtains electrode B thus.Electrode B is struck out the circle of diameter 12mm, used as positive pole B.
Electrode 1 is soaked in the aqueous solution comprising the ascorbic acid of 77mM, the lithium hydroxide of 75mM, and makes it react 5 minutes with 80 DEG C.Then, the pure water by soaking into reacted electrode 1 (hereinafter referred to as electrode 1c) in 60 DEG C washs for 5 minutes.Drying is carried out to the electrode 1c after washing, and carries out the heat treated of 10 hours with 170 DEG C under vacuo.Electrode 1c after heat treated is pressed, obtains electrode C thus.Electrode C is struck out the circle of diameter 12mm, used as positive pole C.
Electrode 1 is soaked in the aqueous solution comprising the ascorbic acid of 77mM, the lithium hydroxide of 75mM, and makes it react 15 minutes with 80 DEG C.Then, the pure water by soaking into reacted electrode 1 (hereinafter referred to as electrode 1d) in 60 DEG C washs for 5 minutes.Drying is carried out to the electrode 1d after washing, and carries out the heat treated of 10 hours with 170 DEG C under vacuo.Electrode 1d after heat treated is pressed, obtains electrode D thus.Electrode D is struck out the circle of diameter 12mm, used as positive pole D.
Electrode 1 is soaked in the aqueous solution comprising the ascorbic acid of 77mM, the lithium hydroxide of 75mM, and makes it react 1 hour with 80 DEG C.Then, the pure water by soaking into reacted electrode 1 (hereinafter referred to as electrode 1e) in 60 DEG C washs for 5 minutes.Drying is carried out to the electrode 1e after washing, and carries out the heat treated of 10 hours with 170 DEG C under vacuo.Electrode 1e after heat treated is pressed, obtains electrode E thus.Electrode E is struck out the circle of diameter 12mm, used as positive pole E.
Electrode 1 is soaked in the aqueous solution comprising the ascorbic acid of 77mM, the lithium hydroxide of 75mM, and makes it react 15 minutes with 60 DEG C.Then, the pure water by soaking into reacted electrode 1 (hereinafter referred to as electrode 1f) in 60 DEG C washs for 5 minutes.Drying is carried out to the electrode 1f after washing, and carries out the heat treated of 10 hours with 170 DEG C under vacuo.Electrode 1f after heat treated is pressed, obtains electrode F thus.Electrode F is struck out the circle of diameter 12mm, used as positive pole F.
When being soaked into by electrode 2 in the aqueous solution comprising the ascorbic acid of 77mM, the lithium hydroxide of 75mM and make it react with 80 DEG C, in reducing solution, active material layer and collector are peeled off.Therefore, about electrode 2, just finish to this stage.
In positive pole A, active material layer weight is 13.7mg, and active material layer thickness is 66 μm.Not considering weight change when being changed to RGO from graphene oxide, namely with the active material ratio in active material layer for 94.2wt% calculate time, area is 1.13cm
2, active material weight is 12.9mg, and active material layer density is 1.84g/cm
3.
In positive pole B, active material layer weight is 13.7mg, and active material layer thickness is 66 μm.Not considering weight change when being changed to RGO from graphene oxide, namely with the active material ratio in active material layer for 94.2wt% calculate time, area is 1.13cm
2, active material weight is 12.3mg, and active material layer density is 1.87g/cm
3.
In positive pole C, active material layer weight is 13.1mg, and active material layer thickness is 62 μm.Not considering weight change when being changed to RGO from graphene oxide, namely with the active material ratio in active material layer for 94.2wt% calculate time, area is 1.13cm
2, active material weight is 12.6mg, and active material layer density is 1.91g/cm
3.
In positive pole D, active material layer weight is 13.3mg, and active material layer thickness is 62 μm.Not considering weight change when being changed to RGO from graphene oxide, namely with the active material ratio in active material layer for 94.2wt% calculate time, area is 1.13cm
2, active material weight is 12.9mg, and active material layer density is 1.89g/cm
3.
In positive pole E, active material layer weight is 13.1mg, and active material layer thickness is 65 μm.Not considering weight change when being changed to RGO from graphene oxide, namely with the active material ratio in active material layer for 94.2wt% calculate time, area is 1.13cm
2, active material weight is 12.3mg, and active material layer density is 1.78g/cm
3.
In positive pole F, active material layer weight is 13.2mg, and active material layer thickness is 62 μm.Not considering weight change when being changed to RGO from graphene oxide, namely with the active material ratio in active material layer for 94.2wt% calculate time, area is 1.13cm
2, active material weight is 12.5mg, and active material layer density is 1.89g/cm
3.
< battery behavior >
Use positive pole A to F as positive pole, use Li metal as negative pole, use the LiPF comprising 1M as electrolyte
6the electrolyte (EC:DEC=1vol:1vol) of EC/DEC, and use porous polypropylene as barrier film, manufacture 2032 type coin batteries thus.Using each coin battery as coin battery A to F.
Measure the charge-discharge characteristic (25 DEG C) of coin battery A to F.That is, with constant current (about 0.4mA) charging and with constant voltage (4.3V) charging, then with constant current discharge.In each coin battery, the charge rate of every positive active material weight is set as 0.2C and charges.
At this, charge rate and discharge rate are described.Such as, when carrying out constant current charge to the secondary cell of capacity X [Ah], the current value I [A] that the end that charge rate 1C refers to charging needs 1 hour, charge rate 0.2C refer to I/5 [A] (that is, to the current value that the end of charging needs 5 hours).Similarly, the current value I [A] that the end that discharge rate 1C refers to electric discharge needs 1 hour, discharge rate 0.2C refer to I/5 [A] (that is, to the current value that the end of electric discharge needs 5 hours).
In the present embodiment, positive active material capacity is assumed to be 170mAh/g, and current value when calculating charging.That is, charge rate 0.2C refers to current value to be the situation that 34mA/g carries out charging.In addition, discharge rate 0.2C refers to current value to be the situation that 34mA/g carries out discharging.In addition, discharge rate 1C refers to current value to be the situation that 170mA/g carries out discharging.In addition, discharge rate 10C refers to current value to be the situation that 1.7A/g carries out discharging.
Discharge curve when Figure 12 illustrates that the discharge rate of coin battery A, B, E is 0.2C, 1C, 10C.The shape of each discharge curve does not make a big difference.The discharge curve of coin battery A, B is roughly consistent, and especially when the high rate discharge of 10C the discharge capacity of coin battery E larger than coin battery A, B.
The discharge capacity of every positive active material weight when table 1 illustrates that the discharge rate of coin battery A to F is 1C and 10C.
[table 1]
When comparing the coin battery C to E only changing the recovery time when manufacturing positive pole, known discharge capacity depends on the recovery time.In addition, the recovery time of coin battery D, F is all 15 minutes, but coin battery D, F to have with the recovery time be the equal discharge capacity of coin battery A, B of 1 hour.
< peeling force test >
Implement adhesive tape 180 ° of disbonded tests (relevant specification ISO29862:2007) of electrode A, B.Specifically, fixing active material layer, and make it peel off from active material layer by hauling collector to the direction of 180 °, determine the strength (peeling force) required for stripping.As mentioned above, the difference of electrode A and electrode B is the cleaning solvent used after electronation.
The peeling force of electrode A is 0.97N, and the peeling force of electrode B is 1.70N.Can think thus: in pure water, peeling force is increased by being soaked into by electrode, thus make electrode be not easy to peel off in the interface of collector and active material layer.
<ToF-SIMS analyzes >
By time of flight secondary ion massspectrometry analysis (ToF-SIMS:Time-of-FlightSecondaryIonMassSpectrometry), electrode A and electrode B are analyzed.As mentioned above, the difference of electrode A and electrode B is the cleaning solvent used after electronation.Note, in ToF-SIMS analyzes, because ascorbic acid and derivative thereof are due to interfering ion, so can not be analyzed.
Figure 13 A to Figure 14 D illustrates the analysis result of ToF-SIMS.C
3h
2f
3ion and C
3hF
4the peak value of ion detects more than electrode B in electrode A.Can think that these ion sources are in PVdF.The peak value of the Cl ion of halide ion and the C of hydrocarbon ion
7h
7the peak value of ion detects more than electrode A in electrode B.In addition, although not shown in the data, in electrode B, C
3h
2f
3ion and C
3hF
4the detection limit of the peak value of ion is different according to measurement place.These results represent, there occurs the modification of PVdF, namely there occurs hydrofluoric disengaging.More specifically, can infer, owing to being captured at hydrofluoric disengaging rear impurity Cl, therefore detect more Cl ion.Can infer, by making hydrogen fluoride depart from, part generates polyene structure.Can think, the polyene structure generated is generated aromatic ring structure by cyclisation.Can also think, the aromatic ring of polyene structure as cyclisation in ToF-SIMS analyzes is detected.All Li is detected in electrode A and electrode B
2oH ion and Li
3the peak value of O ion.The Li detected in electrode A
3the peak value of O ion is more a little than electrode B.Can think that this is the clean result of water, but there is no marked difference.It can thus be appreciated that this is not simple clean result, and may be the impact of the modification of PVdF.
The mensuration > of < electrode resistance
The sheet resistance that Needles method determines electrode A, E, F is visited by four terminals four.That is, active material layer is peeled off from collector, determine the sheet resistance of the active material layer on insulator.As mentioned above, the difference of electrode A and electrode E, F reduces solvent and wash conditions, and the difference of electrode E and electrode F is reduction temperature and time.
The sheet resistance of electrode A, E, F is respectively 450 Ω cm, 11 Ω cm, 290 Ω cm.That is, the resistance ratio electrode A of the electrode E of fully reduction is in aqueous low more than 10 times.In addition, as battery behavior, also as mentioned above, discharge capacity during high rate discharge (10C) of electrode E is larger than electrode A.Therefore, this represents that this battery behavior and this sheet resistance may be relevant.Electrode 1 only comprises graphene oxide as the material that may become conductive auxiliary agent.Therefore, by reducing in aqueous and using pure water, the resistance of Graphene (RGO) can be reduced.Can think this is because the decline of resistance of each graphene platelet self, or because the decline of the resistance between graphene platelet.In the former case, the electrode comprising Graphene is improved because of soaking into performance in the aqueous solution.Can infer: also can improve when this performance is also soaked in the aqueous solution except when utilizing reducing agent to reduce after the reduction utilizing reducing agent.In the latter case, can think this is because contact condition is improved.In other words, the bond state between the adhesive of each particle that bonds (comprising the active material particle of RGO) and each particle is improved and makes the bonding grow between each particle, and the contact resistance thus between each particle is reduced.If consider like this, then also there is impact when the metal forming covered by carbon particle is used as collector to the contact resistance between collector and active material layer.Note, the contact resistance in the early stage between collector and active material layer is fully low, therefore usually can not become problem.Sometimes observe the stripping between collector and active material layer in keeping or after Long-Time Service, and this contact resistance can have influence on cycle characteristics and useful life (preservation characteristics).
< conclusion >
In the present embodiment, the impact of the PVdF of modification and the combination of Graphene has been investigated.It can thus be appreciated that: produce polyene structure or aromatic ring structure due to the modification of PVdF, and, the modification of this PVdF because with comprise pure water the aqueous solution contact and occur.
Symbol description
100 storage battery electrodes
101 collectors
102 active material layers
103 active materials
104 graphene platelets
300 storage batterys
301 positive pole tanks
302 cathode pots
303 pads
304 positive poles
305 plus plate current-collecting bodies
306 positive electrode active material layers
307 negative poles
308 negative current collectors
309 negative electrode active material layers
310 barrier films
500 storage batterys
501 plus plate current-collecting bodies
502 positive electrode active material layers
503 positive poles
504 negative current collectors
505 negative electrode active material layers
506 negative poles
507 barrier films
508 electrolyte
509 external packing bodies
600 storage batterys
601 positive cover
602 battery cans
603 positive terminals
604 positive poles
605 barrier films
606 negative poles
607 negative terminals
608 insulation boards
609 insulation boards
610 pads (insulation spacer)
611PTC element
612 relief valve mechanism
700 display unit
701 frameworks
702 display parts
703 loud speaker portions
704 storage batterys
710 lighting devices
711 frameworks
712 light sources
713 storage batterys
714 ceilings
715 sidewalls
716 floors
717 windows
720 indoor sets
721 frameworks
722 air outlets
723 storage batterys
724 off-premises stations
730 electric household refrigerator-freezers
731 frameworks
732 refrigerating-chamber doors
733 refrigerating chamber doors
734 storage batterys
800 tablet terminal
801 frameworks
802 display parts
802a display part
802b display part
803 display mode diverter switches
804 mains switches
805 battery saving mode diverter switches
807 console switchs
The region of 808a touch-screen
The region of 808b touch-screen
809 operation keyss
810 keyboard & display switching push buttons
811 solar cells
850 charge-discharge control circuits
851 batteries
852DCDC transducer
853 transducers
860 electric automobiles
861 batteries
862 control circuits
863 drive units
864 processing unit
Claims (20)
1. an electrode, comprising:
Active material particle;
Graphene; And
The Kynoar of partial dehydrogenfluoride,
Wherein, the Kynoar of described partial dehydrogenfluoride comprises at least one in polyene structure and aromatic ring structure.
2. electrode according to claim 1,
Wherein said polyene structure or described aromatic ring structure are arranged in the main chain of the Kynoar of described partial dehydrogenfluoride.
3. electrode according to claim 1, wherein said active material particle comprises lithium.
4. a storage battery, comprising:
Electrode according to claim 1; And
Electrolyte.
5. an electronic equipment, comprising:
Storage battery according to claim 4; And
Framework, display unit or switch.
6. an electrode, comprising:
Active material layer, comprising:
Active material particle; And
The Kynoar of partial dehydrogenfluoride; And
Collector, comprising:
Metal level; And
Comprise the layer of carbon particle,
Wherein, the Kynoar of described partial dehydrogenfluoride comprises at least one in polyene structure and aromatic ring structure.
7. electrode according to claim 6,
Wherein said polyene structure or described aromatic ring structure are arranged in the main chain of the Kynoar of described partial dehydrogenfluoride.
8. electrode according to claim 6, wherein said active material particle comprises lithium.
9. a storage battery, comprising:
Electrode according to claim 6; And
Electrolyte.
10. an electronic equipment, comprising:
Storage battery according to claim 9; And
Framework, display unit or switch.
11. a manufacture method for electrode, comprises the steps:
Form the mixture comprising active material particle, graphene oxide and Kynoar;
Described mixture is set on a current collector; And
By processing described mixture in the solution comprising polar solvent and reducing agent, dehydrofluorination is carried out to described Kynoar.
The manufacture method of 12. electrodes according to claim 11, wherein said polar solvent comprises at least one in water, methyl alcohol, ethanol, acetone, oxolane, dimethyl formamide, 1-Methyl-2-Pyrrolidone and dimethyl sulfoxide (DMSO).
The manufacture method of 13. electrodes according to claim 11, wherein said reducing agent has more than-5.0eV and the material of lumo energy below-3.8eV.
The manufacture method of 14. electrodes according to claim 11, wherein said reducing agent comprises ascorbic acid, hydrazine, dimethylhydrazine, hydroquinones, TBAB, NaBH
4and at least one in N, N-diethyl hydroxylamine.
The manufacture method of 15. electrodes according to claim 11,
Wherein in described Kynoar, form polyene structure or aromatic ring structure by described dehydrofluorination.
The manufacture method of 16. 1 kinds of electrodes, comprises the steps:
Form layer on the metal layer, described layer comprises carbon particle;
Form the mixture comprising active material particle and Kynoar;
Described mixture is set on said layer; And
By processing described mixture in the solution comprising polar solvent and reducing agent, dehydrofluorination is carried out to described Kynoar.
The manufacture method of 17. electrodes according to claim 16, wherein said polar solvent comprises at least one in water, methyl alcohol, ethanol, acetone, oxolane, dimethyl formamide, 1-Methyl-2-Pyrrolidone and dimethyl sulfoxide (DMSO).
The manufacture method of 18. electrodes according to claim 16, wherein said reducing agent has more than-5.0eV and the material of lumo energy below-3.8eV.
The manufacture method of 19. electrodes according to claim 16, wherein said reducing agent comprises ascorbic acid, hydrazine, dimethylhydrazine, hydroquinones, TBAB, NaBH
4and at least one in N, N-diethyl hydroxylamine.
The manufacture method of 20. electrodes according to claim 16,
Wherein in described Kynoar, form polyene structure or aromatic ring structure by described dehydrofluorination.
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| CN112289978A (en) * | 2020-06-03 | 2021-01-29 | 大连理工大学 | Composite lithium metal negative electrode and preparation method thereof |
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| US20210119213A1 (en) * | 2017-12-21 | 2021-04-22 | Michael A. Zimmerman | Battery electrode with solid polymer electrolyte and aqueous soluble binder |
| JP7399407B2 (en) * | 2019-09-04 | 2023-12-18 | 時空化学株式会社 | Pouch type supercapacitor, positive electrode material and negative electrode material |
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| US11165066B2 (en) | 2021-11-02 |
| US20220045330A1 (en) | 2022-02-10 |
| JP2020155409A (en) | 2020-09-24 |
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| JP2024032947A (en) | 2024-03-12 |
| JP2022103407A (en) | 2022-07-07 |
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| US11735738B2 (en) | 2023-08-22 |
| CN105322173B (en) | 2020-08-04 |
| CN111710870A (en) | 2020-09-25 |
| JP2016006767A (en) | 2016-01-14 |
| US20150349345A1 (en) | 2015-12-03 |
| KR20150138049A (en) | 2015-12-09 |
| KR20230079338A (en) | 2023-06-07 |
| JP6745587B2 (en) | 2020-08-26 |
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